JP2003195440A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, excellent graininess and little residual color after processing in rapid processing and less liable to lowering of sensitivity after storage. <P>SOLUTION: The silver halide photographic sensitive material contains at least one of the compounds of formulae (Ia)-(Ic) and at least one compound of formula (II) in an emulsion layer, wherein Z<SP>1</SP>is S, O, Se, The, N or C; R, R<SP>31</SP>and R<SP>32</SP>are each alkyl, aryl or a heterocyclic group; D is a group required to form a methine dye; Ra and Rb are each alkyl; V<SP>1</SP>and V<SP>2</SP>are each H or a substituent; M and M<SP>3</SP>are each a counter ion equilibrated with an electric charge; m and m<SP>3</SP>are each a number of ≥0 required to neutralize electric charges in each molecule; Z<SP>31</SP>and Z<SP>32</SP>are each a group of atoms required to form an N-containing heterocycle; L<SP>31</SP>-L<SP>37</SP>are each methine; p<SP>31</SP>and p<SP>32</SP>are each 0 or a; and n<SP>3</SP>is 0, 1, 2, 3 or 4. The compound of the formula (II) is excluded from the compounds of the formulae (Ia)-(Ic). <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a silver halide photograph.
Emulsion and silver halide photographic light-sensitive material containing the emulsion
Is. In more detail, high sensitivity and excellent graininess
Even after rapid processing, there is little residual color after processing, and storage stability
Is to provide a silver halide photographic light-sensitive material having good quality.
The [0002] Sensitizing dyes used for spectral sensitization
Greatly affects the performance of silver halide photographic materials.
It is known that For sensitizing dyes, structurally
There are slight differences in sensitivity, covering, storage stability, and residual after processing.
Significant influence on photographic performance such as existing color (residual color) and graininess
Or by using two or more sensitizing dyes in combination
Although it has a large effect on photographic performance, its effect is predicted in advance.
It is difficult to measure and many researchers have traditionally been
Of various sensitizing dyes and the combination of many sensitizing dyes
I have tried to investigate the photographic performance. But depending
However, the current situation is that we cannot predict photographic performance.
is there. While photographs require high sensitivity and high image quality,
Demand for faster true processing and reduction of waste liquid volume for environmental problems
In recent years, demand has become particularly strong, and negative effects such as residual colors have occurred.
Spectrally sensitize silver halide grains with high sensitivity
Technology is becoming increasingly important. Tabular grains are body
Large surface area (specific surface area) relative to product, with many sensitizing dyes
It is preferable for spectral sensitization in that it can be adsorbed in an amount, and sensitivity
/ It is effective for improving the grain ratio, but it is the color after processing.
Residual color (residual color) increases and the residual color problem is regular
More serious than particles. On the other hand, in photo processing
Although it is desired to reduce the time, the processing time is reduced.
Then, the remaining amount of sensitizing dye used in the emulsion increases.
However, the problem of residual color becomes more serious. Therefore, the remaining color
There is a strong demand for technology to reduce this. As a means to improve the remaining color
It is effective to increase the hydrophilicity of the sensitizing dye
As is generally known, the higher the hydrophilicity, the higher the sensitivity of the sensitizing dye.
Adsorption to silver halide grains is weak, so sensitivity is not reduced.
It is unavoidable to adversely affect photographic properties and is limited to residual color improvement effects.
There was a degree. Also, especially for tabular grains, a large amount of sensitization
When a dye is added, the sensitizing dye adsorbed at a high coverage
More protective colloidal properties of gelatin are impaired,
In the case of tabular grains with a high spectral ratio, the main planes are in contact with each other.
The particles are more likely to agglomerate.
It is clear that side effects such as deterioration of graininess occur
It has become. Solutions to these problems include:
As described in JP-A-6-320991
Halogenated qualitatively insoluble silver iodobromide fine grain emulsion
Known to be added during or after chemical sensitization of silver emulsion.
However, this method can be applied to any emulsion.
But not particularly in high silver chloride emulsions
Therefore, an alternative method was sought. [0003] The problem to be solved by the present invention is high sensitivity.
Excellent in graininess and residual color after processing even in rapid processing
Providing few silver halide photographic materials with good storage stability
There is to serve. [0004] [Means for Solving the Problems] The subject of the present invention is earnest research.
As a result, it can be achieved by the following means:
Came. That is, (1) At least one layer of halo on the support
Silver halide photographic material containing a silver halide photographic emulsion layer
In the composition, the following general formulas (Ia) and (I
b) and a small amount selected from the compounds represented by (Ic)
At least one compound represented by the following general formula (II)
Halogen characterized by containing at least one product
Silver halide photographic material. [0006] [Chemical 3] In the formula (I), Z¹ Is a sulfur atom, an oxygen atom,
Lists selenium, tellurium, nitrogen, or carbon atoms
The R represents an alkyl group, an aryl group or a heterocyclic group.
The D represents a group necessary for forming a methine dye. R
a and Rb each represents an alkyl group. V¹ And V²
Each represents a hydrogen atom or a monovalent substituent. M is charge balance
Represents a counter ion, m to neutralize the charge in the molecule
Represents a required number of zero or more. Formula (II) [0008] [Formula 4] In the formula (II), Z³¹And Z³²Each contains nitrogen
This represents a group of atoms necessary for forming a heterocycle. However,
These rings may be condensed or have a substituent.
Yes. R ³¹And R³²Are each an alkyl group, an aryl group or
Represents a heterocyclic group. L³¹, L³², L³³, L³⁴, L³⁵, L
³⁶And L³⁷Each represents a methine group. p³¹And p³²Is
Each represents 0 or 1. n^ThreeIs 0, 1, 2, 3 or 4
Represents. M^ThreeRepresents a charge balanced counter ion and m^ThreeIs in the molecule
It represents a number of 0 or more necessary for neutralizing the electric charge. However
The compound represented by the general formula (II) is a compound represented by the general formula (I
a), (Ib), and (Ic)
It was. (2) General formula (Ia), (Ib) or (I
In c), D is necessary to form a cyanine dye.
A silver halide copy as described in (1), which is a group
True photosensitive material. (3) General formulas (Ia) and (I
In b) or (Ic), D is represented by D1 below.
The silver halide photographic light-sensitive material as described in (1)
material. [0011] [Chemical formula 5] D¹ Medium, R¹²Is an alkyl group or an aryl group
Or represents a heterocyclic group. Z¹¹Form nitrogen-containing heterocycles
Represents a group of atoms necessary for the
It may have a substituent. L¹¹, L¹², L¹³, L¹⁴And
And L¹⁵Each represents a methine group. p¹Is 0 or 1
Represent. n¹Represents 0, 1, 2, 3 or 4. (4) General formula (Ia), (Ib), or (1)
In (Ic), R is an alkyl group substituted with an acid group.
D is D² (1) characterized in that
The silver halide photographic light-sensitive material described. [0013] [Chemical 6] D²Medium, R^{twenty two}Is an alkyl group substituted by an acid group
Represents. X^{twenty two}Is a sulfur atom, oxygen atom, selenium atom,
Represents a sulfur atom, a nitrogen atom, or a carbon atom. V^{twenty one}, V^{twenty two},
V^{twenty three}And V^{twenty four}Each represents a hydrogen atom or a substituent. However
V^{twenty one}, V^{twenty two}, V^{twenty three}And V^{twenty four}2 adjacent to each other
Two substituents linked together to form a saturated or unsaturated fused ring
Or aromatic groups, and aromatic hetero
It is not a cyclic group. L^{twenty one}, L^{twenty two}And L^{twenty three}Is that
Represents a methine group. n²Represents 0 or 1. (5) General formulas (Ia) and (I
b) or (Ic), wherein R is an alkyl group substituted with an acid group
Kill group, D is D^ThreeOr D^FourSpecially represented by
The silver halide photographic light-sensitive material as described in (1). [0016] [Chemical 7] D^Three Medium, R³²Is an alkyl group substituted by an acid group
Represents. X³²Represents a sulfur atom or an oxygen atom. V³²Is
Represents a halogen atom. D^Four Medium, R⁴²Is the acid group substituted
Represents an alkyl group. X⁴²Represents a sulfur atom or an oxygen atom
The V⁴²Represents a halogen atom. (6) General formulas (Ia) and (I
b) or (Ic), X⁴²Represents an oxygen atom
The silver halide photographic light-sensitive material as described in (5) above
Fee. (7) General formulas (Ia) and (I
b) or (Ic), D is D^Three Represented by
The silver halide photographic light-sensitive material as described in (5)
Fee. (8) The silver halide described in (1) to (7)
In the photographic light-sensitive material, the general formula (Ia)
Is at least one of the compounds represented by (Ib),
And at least one compound represented by formula (II)
A silver halide photographic light-sensitive material comprising: (9) The general formula (I) described in (1) to (8)
In a), (Ib) or (Ic), Ra and Rb
(1) to (8) characterized in that is a methyl group
The silver halide photographic light-sensitive material described in any one of the above. (10) The general formula (I) described in (1) to (9)
In a), (Ib) or (Ic), Z¹ Is a sulfur atom
Any one of (1) to (9), characterized in that
The silver halide photographic light-sensitive materials listed. (11) General formulas described in (1) to (10)
(II) is selected from the following general formula (IIa)
The silver halide according to any one of (1) to (10)
Photosensitive material. Formula (IIa) [0024] [Chemical 8] In the formula (IIa), X⁴¹And X⁴²Each is sulfur
Atoms, oxygen atoms, selenium atoms, tellurium atoms, nitrogen atoms,
Or represents a carbon atom. V⁴¹, V⁴², V⁴³, V⁴⁴, V⁴⁵,
V⁴⁶, V⁴⁷And V⁴⁸Each represents a hydrogen atom or a substituent.
Two adjacent substituents linked together and saturated or
An unsaturated condensed ring may be formed. R⁴¹And R⁴²Is
Each represents an alkyl group, an aryl group or a heterocyclic group. L
⁴¹, L⁴²And L⁴³Each represents a methine group. n^FourIs 0,
1, 2, 3 or 4 is represented. M^FourRepresents a counter ion, m^Four
Is a number greater than or equal to zero necessary to neutralize the charge in the molecule
Represent. (12) General formulas described in (1) to (10)
Whether (II) is the following general formula (III) or the following general formula (IV)
Any one of (1) to (10),
2. A silver halide photographic light-sensitive material as described above. General formula (III) [0027] [Chemical 9] In the formula (III), X⁵¹And X⁵²Are each oxygen
Represents an atom or a sulfur atom. V⁵¹, V⁵², V⁵³, V⁵⁴,
V⁵⁵And V⁵⁶Each represents a hydrogen atom or a substituent,
Two adjacent substituents are connected to each other to be saturated or unsaturated
The condensed ring is not formed. R⁵¹, R⁵²And R⁵³
Each represents an alkyl group, an aryl group or a heterocyclic group.
M^FiveRepresents a counter ion, m^FiveNeutralizes charge in the molecule
This represents a number of 0 or more necessary for the purpose. Formula (IV) [0029] Embedded image In the formula (IV), X⁶¹Is oxygen atom or sulfur source
Represents a child. V⁶¹, V⁶², V⁶³, V⁶⁴, V⁶⁵And V⁶⁶Is
Each represents a hydrogen atom or a substituent, and two adjacent substitutions
Groups are linked together to form a saturated or unsaturated fused ring
Never happen. R⁶¹And R ⁶²Each is an alkyl group,
Represents a hydroxyl group or a heterocyclic group. M⁶Represents the counter ion,
m⁶Is greater than zero required to neutralize the charge in the molecule
Represents a number. (13) General formula (III) described in (12)
X⁵¹And X⁵²Are both sulfur atoms
The silver halide photographic photosensitive material as described in (12) above
material. (14) Silver halide photograph described in (12)
In photosensitive materials, general formula (II) is selected from general formula (IV).
The silver halide according to (12), characterized in that
Photosensitive material. (15) In the emulsion layer according to (1) to (14), milk
50% or more of the total projected area of silver halide grains in the agent
It is a tabular grain having a spect ratio of 2 or more
The silver halide photograph according to any one of (1) to (14)
Photosensitive material. (16) The emulsion layer described in (1) to (15)
In which the emulsion is selenium-sensitized.
The silver halide copy according to any one of (1) to (15)
True photosensitive material. [0034] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
In the present invention, when a specific part is referred to as a “group”
Is a kind even if the part itself is not substituted
Substituted with the above (up to the maximum possible) substituents
Also means good. For example, `` alkyl group ''
A substituted or unsubstituted alkyl group is meant. In addition, the present invention
Substituents that can be used for compounds in
Regardless, any substituent is included. When such a substituent is represented by V, it is represented by V.
Any substituent may be used, and particularly limited.
For example, a halogen atom, an alkyl group [(
Loalkyl group, bicycloalkyl group, tricycloalkyl
Alkenyl group (cycloalkenyl)
Groups, including bicycloalkenyl groups), alkynyl groups, and
To include. ], Aryl group, heterocyclic group (heterocycle
Group), cyano group, hydroxyl group, nito
B group, carboxyl group, alkoxy group, aryloxy
Group, silyloxy group, heterocyclic oxy group, acyloxy
Group, carbamoyloxy group, alkoxycarbonyloxy
Si group, aryloxycarbonyloxy group, amino group
(Including anilino group), ammonio group, acylamino
Group, aminocarbonylamino group, alkoxycarbonyl
Amino group, aryloxycarbonylamino group, sulf
Amoylamino, alkyl and arylsulfonyl groups
Mino group, mercapto group, alkylthio group, arylthio
Group, heterocyclic thio group, sulfamoyl group, sulfo group,
Alkyl and arylsulfinyl groups, alkyl and ant
Arylsulfonyl group, acyl group, aryloxycarboni
Group, alkoxycarbonyl group, carbamoyl group, ant
And azo, imide, phosphino,
Sufinyl group, phosphinyloxy group, phosphinyl group
Mino group, phosphono group, silyl group, hydrazino group, urei
Group, boronic acid group (-B (OH)<sub>2</sub> ), Phosphato groups (-OPO (O
H)<sub>2</sub>), Sulfato groups (-OSO<sub>Three</sub>H) Other known substitutions
The group is given as an example. More specifically, V is a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, iodine atom),
Alkyl group [straight chain, branched, cyclic substituted or unsubstituted
Represents an alkyl group. They are alkyl groups (preferably
Alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl
, N-propyl, isopropyl, t-butyl, n-o
Cutyl, eicosyl, 2-chloroethyl, 2-cyanoe
Til, 2-ethylhexyl), cycloalkyl group (preferably
Or a substituted or unsubstituted cyclohexane having 3 to 30 carbon atoms.
Alkyl groups such as cyclohexyl, cyclopentyl
, 4-n-dodecylcyclohexyl), bicycloal
A kill group (preferably a substitution of 5 to 30 carbon atoms or
Unsubstituted bicycloalkyl group, ie, having 5 to 3 carbon atoms
One hydrogen atom removed from 0 bicycloalkane
Is a valent group. For example, bicyclo [1,2,2] hepta
N-2-yl, bicyclo [2,2,2] octane-3-
Yl) and tricyclo structures with more ring structures
Is. Alkyl groups in the substituents described below
(For example, an alkyl group of an alkylthio group)
Represents the intended alkyl group, but also alkenyl group, alkyl
Nyl group is also included. ], Alkenyl group [straight chain, minute
Represents a cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
Substituted or unsubstituted alkenyl groups such as vinyl,
Allyl, prenyl, geranyl, oleyl), cycloal
A kenyl group (preferably a substitution of 3 to 30 carbon atoms or
Is an unsubstituted cycloalkenyl group, that is, from 3 carbon atoms
Monovalent with 30 hydrogen atoms removed from cycloalkene
It is the basis of. For example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), bicycloalkenyl
Group (substituted or unsubstituted bicycloalkenyl group, preferably
Or a substituted or unsubstituted bismuth having 5 to 30 carbon atoms.
Chloalkenyl group, that is, bicyclo with one double bond
It is a monovalent group with one hydrogen atom of the alkene removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl). ], An alkynyl group (preferably
Preferably, the substituted or unsubstituted alkyl having 2 to 30 carbon atoms
Quinyl groups, such as ethynyl, propargyl, trimethyl
Rusilylethynyl group)], aryl group (preferably carbon
A substituted or unsubstituted aryl group of formula 6 to 30, for example
Phenyl, p-tolyl, naphthyl, m-chloropheny
, O-hexadecanoylaminophenyl), heterocyclic group
(Preferably 5 or 6 membered substituted or unsubstituted, good
One hydrogen source from an aromatic or non-aromatic heterocyclic compound
A monovalent group with the child removed, more preferably carbon
A 5- or 6-membered aromatic heterocyclic group of 3 to 30
The For example, 2-furyl, 2-thienyl, 2-pyrimidi
Nyl, 2-benzothiazolyl, 1-methyl-2-
Pyridinio, 1-methyl-2-quinolinio
An on-ring heterocyclic group may be used. ), Cyano group, hydroxy
Group, nitro group, carboxyl group, alkoxy group (preferred
Or a substituted or unsubstituted alkyl having 1 to 30 carbon atoms.
Coxy groups such as methoxy, ethoxy, isopropoxy
Si, t-butoxy, n-octyloxy, 2-methoxy
Ethoxy), an aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, eg
For example, phenoxy, 2-methylphenoxy, 4-t-butyl
Tylphenoxy, 3-nitrophenoxy, 2-tetrade
Canoylaminophenoxy), silyloxy group (preferred
Or a silyloxy group having 3 to 20 carbon atoms such as
Limethylsilyloxy, t-butyldimethylsilyloxy
Ii) a heterocyclic oxy group (preferably having 2 to 3 carbon atoms)
0 substituted or unsubstituted heterocyclic oxy group, 1-phen
Nyltetrazol-5-oxy, 2-tetrahydropyra
Nyloxy), acyloxy groups (preferably formylio)
Xyl group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms
Kill carbonyloxy group, substitution of 6 to 30 carbon atoms
Or an unsubstituted arylcarbonyloxy group such as
Lumiloxy, acetyloxy, pivaloyloxy,
Thearoyloxy, benzoyloxy, p-methoxyph
Enylcarbonyloxy), carbamoyloxy group (preferably
Preferably, a substituted or unsubstituted carbon having 1 to 30 carbon atoms.
Rubamoyloxy group, for example, N, N-dimethylcarba
Moyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octy
Ruaminocarbonyloxy, Nn-octylcarbamo
Yloxy), alkoxycarbonyloxy group (preferred
Or substituted or unsubstituted alkoxy having 2 to 30 carbon atoms.
Sicarbonyloxy groups such as methoxycarbonyloxy
Si, ethoxycarbonyloxy, t-butoxycarboni
Ruoxy, n-octylcarbonyloxy), aryl
Oxycarbonyloxy group (preferably having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyls
An oxy group such as phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexa
Decyloxyphenoxycarbonyloxy), amino group
(Preferably an amino group, a C 1-30 substituent.
Or an unsubstituted alkylamino group having 6 to 30 carbon atoms.
Substituted or unsubstituted anilino groups such as amino, methyl
Ruamino, dimethylamino, anilino, N-methyl-ani
Lino, diphenylamino), ammonio groups (preferably
Ammonio group, substituted or unsubstituted having 1 to 30 carbon atoms
Ammonio substituted with alkyl, aryl or heterocycle
Groups such as trimethylammonio, triethylammo
Nio, diphenylmethylammonio), acylamino group
(Preferably a formylamino group having 1 to 30 carbon atoms
Substituted or unsubstituted alkylcarbonylamino group, charcoal
Substituted or unsubstituted arylcarbo having a prime number of 6 to 30
Nylamino groups such as formylamino, acetylamido
, Pivaloylamino, lauroylamino, benzoyl
Amino, 3,4,5-tri-n-octyloxypheny
Rucarbonylamino), aminocarbonylamino group (preferably
Preferably, it is a substituted or unsubstituted atom having 1 to 30 carbon atoms.
Minocarbonylamino, such as carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-di
Ethylaminocarbonylamino, morpholinocarbonyl
Amino), an alkoxycarbonylamino group (preferably
C2-C30 substituted or unsubstituted alkoxycal
A bonylamino group, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonyla
Mino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), aryloxy
A carbonylamino group (preferably having 7 to 30 carbon atoms)
Substituted or unsubstituted aryloxycarbonylamino
Groups such as phenoxycarbonylamino, p-chloro
Enoxycarbonylamino, mn-octyloxyphene
Noxycarbonylamino), sulfamoylamino group
(Preferably substituted or unsubstituted having 0 to 30 carbon atoms
A sulfamoylamino group such as sulfamoyla
Mino, N, N-dimethylaminosulfonylamino, N-
n-octylaminosulfonylamino), alkyl and
Arylsulfonylamino group (preferably from 1 carbon atom)
30 substituted or unsubstituted alkylsulfonylamines
No, substituted or unsubstituted aryl having 6 to 30 carbon atoms
Sulfonylamino, such as methylsulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), mercapto group,
Alkylthio groups (preferably substituted with 1 to 30 carbon atoms)
Or an unsubstituted alkylthio group such as methylthio,
Ethylthio, n-hexadecylthio), arylthio group
(Preferably substituted or unsubstituted having 6 to 30 carbon atoms
Arylthio, such as phenylthio, p-chlorophene
Nylthio, m-methoxyphenylthio), heterocyclic thio
Group (preferably substituted or unsubstituted having 2 to 30 carbon atoms)
A heterocyclic thio group such as 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), sulfa
Moyl group (preferably substituted with 0 to 30 carbon atoms or
Unsubstituted sulfamoyl groups such as N-ethylsulf
Amoyl, N- (3-dodecyloxypropyl) sulfur
Amoyl, N, N-dimethylsulfamoyl, N-ace
Tilsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoy
), Sulfo group, alkyl and arylsulfinyl group
(Preferably substituted or unsubstituted having 1 to 30 carbon atoms
Alkylsulfinyl group, substituted or unsubstituted 6 to 30
Substituted arylsulfinyl groups such as methylsulfinyl
Nyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), alkyl and aryl
A rusulfonyl group (preferably a substitution of 1 to 30 carbon atoms)
Or an unsubstituted alkylsulfonyl group, from 6 to 30
Substituted or unsubstituted arylsulfonyl groups such as meth
Rusulfonyl, ethylsulfonyl, phenylsulfoni
, P-methylphenylsulfonyl), acyl group (preferred
Or a formyl group, substituted or non-substituted with 2 to 30 carbon atoms
Substituted alkylcarbonyl groups, and those with 7 to 30 carbon atoms
Or an unsubstituted arylcarbonyl group having 4 to 3 carbon atoms
Bonded to a carbonyl group with zero substituted or unsubstituted carbon atoms
Combined heterocyclic carbonyl groups such as acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, ben
Zoyl, pn-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), a
A reeloxycarbonyl group (preferably having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyls
Groups such as phenoxycarbonyl, o-chloropheno
Xyloxycarbonyl, m-nitrophenoxycarbonyl, p
-T-butylphenoxycarbonyl), alkoxycal
A bonyl group (preferably a C 2-30 substituent or
Is an unsubstituted alkoxycarbonyl group such as methoxy
Rubonyl, ethoxycarbonyl, t-butoxycarbonyl
, N-octadecyloxycarbonyl), carbamoy
(Preferably substituted or non-substituted with 1 to 30 carbon atoms)
Substituted carbamoyl, eg carbamoyl, N-methyl
Rucarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulf
Phonyl) carbamoyl), aryl and heterocyclic azo groups
(Preferably substituted or unsubstituted having 6 to 30 carbon atoms
Arylazo group, substituted or unsubstituted 3 to 30 carbon atoms
Substituted heterocyclic azo groups such as phenylazo, p-chloro
Rophenylazo, 5-ethylthio-1,3,4-thiadi
Azol-2-ylazo), an imide group (preferably N
-Succinimide, N-phthalimide), phosphino group
(Preferably substituted or unsubstituted having 2 to 30 carbon atoms
Phosphino groups such as dimethylphosphino, diphe
Nylphosphino, methylphenoxyphosphino), phos
A finyl group (preferably substituted with 2 to 30 carbon atoms)
Or an unsubstituted phosphinyl group such as phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphini
Or phosphinyloxy group (preferably having 2 carbon atoms)
30 substituted or unsubstituted phosphinyloxy groups,
For example, diphenoxyphosphinyloxy, dioctyl
Oxyphosphinyloxy), phosphinylamino group
(Preferably substituted or unsubstituted having 2 to 30 carbon atoms
A phosphinylamino group such as dimethoxyphosphi
Nylamino, dimethylaminophosphinylamino), pho
Phospho group, silyl group (preferably having 3 to 30 carbon atoms)
Substituted or unsubstituted silyl groups such as trimethyl
Ril, t-butyldimethylsilyl, phenyldimethylsilane
Ryl), a hydrazino group (preferably having 0 to 30 carbon atoms)
Substituted or unsubstituted hydrazino groups such as trimethyl
Ruhydrazino), ureido group (preferably having 0 carbon atoms)
30 substituted or unsubstituted ureido groups such as N, N
-Dimethylureido). In addition, the two Vs are combined to form a ring (aromatic,
Is a non-aromatic hydrocarbon ring or heterocyclic ring. These are more
Can be combined to form a polycyclic fused ring.
For example, benzene ring, naphthalene ring, anthracene ring,
Enanthrene ring, fluorene ring, triphenylene ring, na
Phthacene ring, biphenyl ring, pyrrole ring, furan ring, thi
Offen ring, imidazole ring, oxazole ring, thiazo
Ring, pyridine ring, pyrazine ring, pyrimidine ring,
Dazine ring, indolizine ring, indole ring, benzofura
Ring, benzothiophene ring, isobenzofuran ring, quino
Lysine ring, quinoline ring, phthalazine ring, naphthyridine
Ring, quinoxaline ring, quinoxazoline ring, isoquinoline
Ring, carbazole ring, phenanthridine ring, acridine
Ring, phenanthroline ring, thianthrene ring, chromene
Ring, xanthene ring, phenoxathiin ring, phenothiazi
Ring and phenazine ring. Forming)
You can also. Among the above substituents V, it has a hydrogen atom
Are removed and further substituted with the above groups
Also good. Examples of such substituents include -CONHS
O<sub>2</sub>-Group (sulfonylcarbamoyl group, carbonylsulfuryl group)
Famoyl group), -CONHCO- group (carbonyl cal)
Bamoyl group), -SO<sub>2</sub> NHSO<sub>2</sub> -Group (sulfonyl)
Sulfamoyl group). More specifically,
An alkylcarbonylaminosulfonyl group (for example, ace
Tilaminosulfonyl), arylcarbonylaminos
Sulfonyl groups (eg benzoylaminosulfonyl)
Group), alkylsulfonylaminocarbonyl group (for example,
Methylsulfonylaminocarbonyl), aryls
A sulfonylaminocarbonyl group (for example, p-methylphenyl)
Nylsulfonylaminocarbonyl). The general formulas (Ia) and (Ib)
 ) And methine dyes represented by (Ic)
I will explain. Each of (Ia), (Ib), and (Ic)
Of Z<sup>1</sup>, R, D, V<sup>1</sup> , V<sup>2</sup> , Ra, Rb, M, m are
They may be the same or different. (Ia), (Ib
 ) And (Ic), preferably (Ia) and
(Ib). Z<sup>1</sup> Is a sulfur atom, oxygen atom, selenium
Atoms, tellurium atoms, nitrogen atoms (N-V<sup>a</sup>) Or carbon source
Child (CV<sup>b</sup>V<sup>c</sup>). Where V<sup>a</sup>, V<sup>b</sup>, V<sup>c</sup>Is
A hydrogen atom or a substituent (for example, V described above),
Preferably, a hydrogen atom, an alkyl group, an aryl group, or
It is a heterocyclic group. Alkyl group, aryl group, or heterocycle
Examples of the group include those similar to R described later.
Is preferred. Particularly preferred is an alkyl group. Z
<sup>1</sup> Preferably, sulfur atom, oxygen atom, selenium source
Or a nitrogen atom, more preferably a sulfur atom.
Child, oxygen atom or selenium atom, particularly preferably
A sulfur atom or an oxygen atom, most preferably a sulfur atom
A child. Z<sup>1</sup> Excellent photographic performance especially when is a sulfur atom
Indicates. R is an alkyl group, an aryl group, or a heterocyclic ring
Group, preferably an alkyl group or an aryl group.
Particularly preferred is an alkyl group. Represented as R
Specific examples of alkyl group, aryl group, and heterocyclic group
Thus, for example, 1 to 18 carbon atoms, preferably 1
7, particularly preferably 1 to 4 unsubstituted alkyl groups (eg
For example, methyl, ethyl, propyl, isopropyl, buty
, Isobutyl, hexyl, octyl, dodecyl, octyl
Tadecyl), 1 to 18 carbon atoms, preferably 1 to
7, particularly preferably 1 to 4 substituted alkyl groups {eg
Examples of the substituent include an alkyl group substituted with V described above.
The In particular, the above-described alkyl group having an acid group is preferable.
Preferably an aralkyl group (eg benzyl, 2-phenyl)
Ruethyl), unsaturated hydrocarbon groups (eg allyl groups, vinyl
Group, i.e., here, substituted alkyl groups are alkenyl
Groups and alkynyl groups are also included. ), Hydroxy
Cialkyl groups (eg 2-hydroxyethyl, 3-hydroxy
Droxypropyl), a carboxyalkyl group (for example,
2-carboxyethyl, 3-carboxypropyl, 4-
Carboxybutyl, carboxymethyl), alkoxy
Alkyl group (for example, 2-methoxyethyl, 2- (2-methyl
Toxiethoxy) ethyl), aryloxyalkyl group
(For example, 2-phenoxyethyl, 2- (1-naphthoxy
Ii) ethyl), alkoxycarbonylalkyl groups (eg
For example, ethoxycarbonylmethyl, 2-benzyloxycar
Bonylethyl), aryloxycarbonylalkyl group
(Eg 3-phenoxycarbonylpropyl), acyl
Oxyalkyl groups (eg 2-acetyloxyethyl)
), An acylalkyl group (for example, 2-acetylethyl)
), A carbamoylalkyl group (eg 2-morpholino)
Carbonylethyl), sulfamoylalkyl groups (eg
N, N-dimethylsulfamoylmethyl), sulfoa
Alkyl group (for example, 2-sulfoethyl, 3-sulfopro
Pill, 3-sulfobutyl, 4-sulfobutyl, 2- [3
-Sulfopropoxy] ethyl, 2-hydroxy-3-s
Rufopropyl, 3-sulfopropoxyethoxyethyl
), Sulfoalkenyl groups, sulfatoalkyl groups (eg
For example, 2-sulfatoethyl group, 3-sulfatopropiyl
, 4-sulfatobutyl), a heterocyclic-substituted alkyl group
(Eg 2- (pyrrolidin-2-one-1-yl) ethyl
, Tetrahydrofurfuryl), alkylsulfonylca
Rubamoylalkyl group (eg methanesulfonylcarba
Moylmethyl group), acylcarbamoylalkyl group (eg
Acetylcarbamoylmethyl group), acylsulfa
Moylalkyl groups (eg acetylsulfamoylmethyl)
Group), alkylsulfonylsulfamoylalkyl
Groups (eg methanesulfonylsulfamoylmethyl)
Group)}, 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
0, more preferably 6 to 8 carbon atoms substituted or unsubstituted
Substituted aryl groups (examples of substituents include the aforementioned V
The Specifically, phenyl group, 1-naphthyl group, p-meth
Xiphenyl group, p-methylphenyl group, p-chloroph
Examples include an phenyl group. ), 1 to 20 carbon atoms, good
Preferably 3 to 10 carbon atoms, more preferably 4 carbon atoms
To 8 substituted or unsubstituted heterocyclic groups (examples of substituents)
Includes V described above. Specifically, 2-furyl group, 2
-Thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-
Isoxazolyl, 3-isothiazolyl, 2-imidazo
Ril, 2-oxazolyl, 2-thiazolyl, 2-pyrida
Gills, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-tol
Reazolyl), 3- (1,2,4-triazolyl), 5-teto
Lazolyl, 5-methyl-2-thienyl group, 4-methoxy
And a 2-pyridyl group. ). R is preferably an unsubstituted alkyl group,
Is a substituted alkyl group and is preferred as a substituted alkyl group
Or an alkyl group substituted with an acid group. Where the acid group
explain about. An acid group is a group having a dissociable proton
It is. Specifically, for example, sulfo group, carboxyl
Group, sulfato group, -CONHSO<sub>2</sub> -Group (sulfonyl)
Carbamoyl group, carbonylsulfamoyl group), -C
ONHCO— group (carbonylcarbamoyl group), —SO
<sub>2</sub> NHSO<sub>2</sub> -Group (sulfonylsulfamoyl group),
Sulfonamide group, sulfamoyl group, phosphato group,
Phosphono group, boronic acid group, phenolic hydroxyl group, etc.
Depending on these pka and surrounding pH, protons dissociate
Group to be mentioned. For example, more than 90% dissociation between pH 5-11
Proton dissociable acidic groups that can be preferred. The
More preferably, a sulfo group, a carboxyl group, -CONH
SO<sub>2</sub> -Group, -CONHCO- group, -SO<sub>2</sub> NHSO<sub>2</sub>
-Group, particularly preferably sulfo group, carboxyl
Group, and most preferably a sulfo group. As an alkyl group having an acid group, specifically,
Preferably 3-sulfopropyl group, 4-sulfobutyl
Group, 3-sulfobutyl group, 2-sulfoethyl group, carbo
Xymethyl, carboxyethyl, carboxypropy
A methanesulfonylcarbamoylmethyl group,
Most preferably, 3-sulfopropyl group, 4-sulfobuty
Group, 3-sulfobutyl group, 2-sulfoethyl group, cal
Boxymethyl group, methanesulfonylcarbamoylmethyl
It is a group. Sulfo group, carboxyl group, -CONHS
O<sub>2</sub> -Group, -CONHCO- group, -SO<sub>2</sub> NHSO<sub>2</sub> −
Preferred alkyl groups substituted by groups are those of the formula
Can be expressed as follows. [0044] Embedded imageQ<sup>a</sup>Is required for R to form an alkyl group
A linking group (preferably a divalent linking group). R<sup>a</sup>, R
<sup>b</sup>, R<sup>c</sup>And R<sup>d</sup>Are each an alkyl group, an aryl group,
Heterocyclic group, alkoxy group, aryloxy group, heterocycle
Represents a ryloxy group or an amino group. Q<sup>a</sup>As long as it meets the above requirements
Any linking group may be used, but carbon atom, nitrogen atom, sulfur atom
Atom or atom containing at least one of a child and an oxygen atom
Consists of children. Preferably an alkylene group (eg methyl
, Ethylene, trimethylene, tetramethylene, pentane
Methylene, methyltrimethylene), alkenylene groups (eg
For example, ethenylene, propenylene), alkynylene groups
(E.g., ethynylene, propynylene), amide group, et
Steal group, sulfoamide group, sulfonate group,
Raid group, sulfonyl group, sulfinyl group, thioate
Group, ether group, carbonyl group, -N (V<sup>d</sup>)-(V
<sup>d</sup>Represents a hydrogen atom or a monovalent substituent. Monovalent substitution
Examples of the group include V described above. ), Or one
A combination of 0 or more and 0 to 10 carbon atoms,
Preferably, it represents a linking group having 1 to 5 carbon atoms. The above linking group is further represented by the aforementioned V.
Or a ring (aromatic or non-aromatic).
An aromatic hydrocarbon ring or a heterocyclic ring). However
And these linking groups do not contain heteroatoms.
Is more preferable. In addition, the substituent represented by V described above
The case where it is not substituted with is more preferable. More preferably, the carbon atom has 1 to 5 carbon atoms.
A alkylene group (eg methylene, ethylene, trimethyle)
, Tetramethylene, pentamethylene, methyltrimethyl
), Alkenylene groups having 2 to 5 carbon atoms (for example,
Ethenylene, propenylene), 2 to 5 carbon atoms
An alkynylene group such as ethynylene, propynyl
N), or a combination of one or more carbons
It is a divalent linking group having a number of 1 or more and 5 or less. Especially preferred
Is an alkylene group having 1 to 5 carbon atoms (preferably
Tylene, ethylene, trimethylene, tetramethylene)
is there. X<sup>a</sup>Q is a sulfo group<sup>a</sup>As further
Preferably, ethylene, trimethylene, tetramethyle
And methyltrimethylene, particularly preferably
Tylene. X<sup>a</sup>Q is a carboxyl group<sup>a</sup>When
More preferably, methylene, ethylene, trimethyle
Particularly preferred is methylene. X<sup>a</sup>-CO
NHSO<sub>2</sub>R<sup>a</sup>, SO<sub>2</sub>NHCOR<sup>b</sup>, CONHCOR<sup>c</sup>, SO<sub>2</sub>NHSO<sub>2</sub>R<sup>d</sup>In the case of,
Q<sup>a</sup>More preferably, methylene, ethylene, tri
Methylene, particularly preferably methylene. R<sup>a</sup>, R<sup>b</sup>, R<sup>c</sup>, R<sup>d</sup>Are each alkyl
Group, aryl group, heterocyclic group, alkoxy group, aryloxy
Represents a silyl group, a heterocyclyloxy group, or an amino group
However, the following are preferable. For example, carbon number 1 to 18, preferably charcoal
1 to 10 prime, more preferably 1 to 5 carbon
Substituted alkyl groups (eg methyl, ethyl, propyl,
Butyl), 1 to 18 carbon atoms, preferably 1 to carbon atoms
10, more preferably substituted alkyl having 1 to 5 carbon atoms
Groups (hydroxymethyl, trifluoromethyl, benzyl)
, Carboxyethyl, ethoxycarbonylmethyl, a
Cetylaminomethyl and also preferably here carbon number
2 to 18, more preferably 3 to 10 carbon atoms, especially
Preferably an unsaturated hydrocarbon group having 3 to 5 carbon atoms (for example,
Vinyl group, ethynyl group, 1-cyclohexenyl group, ben
Dilysine group and benzylidene group) are also included in the substituted alkyl group
I will decide. ), Carbon number 6 to 20, preferably charcoal
6 to 15 prime, more preferably 6 to 10 carbon
Substituted or unsubstituted aryl groups (eg phenyl, naphth
Til, p-carboxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-cyanophenyl, m-
Fluorophenyl, p-tolyl), 1 to 20 carbon atoms,
Preferably 2 to 10 carbons, more preferably carbons
4 to 6 optionally substituted heterocyclic groups (eg, pyridi
5, 5-methylpyridyl, thienyl, furyl, morpholy
, Tetrahydrofurfuryl), 1 to 10 carbon atoms, good
Preferably, the alkoxy group having 1 to 8 carbon atoms (for example, methoxy
Si, ethoxy, 2-methoxyethoxy, 2-hydroxy
Ethoxy, 2-phenylethoxy), 6 to 2 carbon atoms
0, preferably 6 to 12 carbons, more preferably charcoal
An aryloxy group having a prime number of 6 to 10 (for example, phenoxy
P-methylphenoxy, p-chlorophenoxy, na
Ftoxy), 1 to 20 carbon atoms, preferably 3 carbon atoms
12, more preferably a heterocycle having 3 to 10 carbon atoms
Kuryloxy group (means an oxy group substituted with a heterocyclic group)
To do. For example 2-thienyloxy, 2-morpholinooxy
B) As an amino group, carbon 0 to 20, preferably charcoal
Prime number 0 to 12, more preferably 0 to 8 carbon atoms
Mino group (eg amino, methylamino, dimethylamido)
, Ethylamino, diethylamino, hydroxyethyl
Amino, benzylamino, anilino, diphenylami
, Morpholino with ring formation, pyrrolidino)
The Furthermore, the above-mentioned V may be substituted for these.
Yes. More preferably, a methyl group, an ethyl group, a hydroxy group
A methyl group, particularly preferably a methyl group. In the acid group, for example, carboxyl
Groups, dissociative nitrogen atoms, etc. are shown in a non-dissociated form
(CO<sub>2</sub> H), (NH), dissociated form (CO
<sub>2</sub> <sup>-</sup>), (N<sup>-</sup>) Or both. actually
Is in a dissociated state due to the pH or other environment where the dye is placed.
Or become non-dissociated. Positive as counter ion
If ions are present, for example (CO<sub>2</sub> <sup>-</sup>, Na<sup>+</sup>),
(N <sup>-</sup>, Na<sup>+</sup>). In non-dissociated state
(CO<sub>2</sub> H) and (NH), but counter ion
If the on-compound is considered as a proton, (CO<sub>2</sub> <sup>-</sup>,
H<sup>+</sup>), (N<sup>-</sup>, H<sup>+</sup>). V<sup>1</sup> And V<sup>2</sup> Are each independently a hydrogen atom,
Or it represents a monovalent substituent. Examples of monovalent substituents include
For example, V mentioned above can be mentioned. Preferred as a monovalent substituent
Is a substituent that is more hydrophilic than the iodine atom, and
Preferably the same as the chlorine atom or a more hydrophilic substitution
It is a group. For example, specifically, bromine atom, chlorine atom,
Fluorine atom, hydroxyl group, carboxyl group, methyl
Group and methoxy group. V<sup>1</sup> And V<sup>2</sup> As the best
Is preferably a hydrogen atom. Ra and Rb are each independently an alkyl group.
Represents. As Ra and Rb, the aforementioned alkyl of R
The thing similar to what was mentioned by description of group is mentioned. Ra
And Rb may together form a ring, eg
Physically, unsubstituted alkylene (eg trimethylene, te
Tramethylene), but such a ring is formed
It is better not to. Preferred as Ra and Rb
Is an unsubstituted alkyl group having 1 to 3 carbon atoms (for example, methyl,
Ethyl, propyl), more preferably methyl,
Ethyl, particularly preferably methyl. M is used to neutralize the ionic charge of the dye.
Indicates the presence of a cation or anion when necessary
Is included in the formula. Some dyes are cations,
Whether it is an anion or has a net ionic charge
How about its substituents and the environment in solution (such as pH)
Depends on. Typical cations include hydrogen ions (H
<sup>+</sup>), Alkali metal ions (for example, sodium ions,
Potassium ion, lithium ion), alkaline earth metal
Inorganic cations such as ions (eg calcium ions)
Ammonium ion (for example, ammonium ion)
, Tetraalkylammonium ions, triethylammonium
Ammonium ion, pyridinium ion, ethyl pyridi
Nium ion, 1,8-diazabicyclo [5.4.0]
Organic ions such as -7-undecenium ion)
It is done. Anions are inorganic or organic anions
Can be any halide anion (eg
For example, fluoride ion, chloride ion, bromide ion, iodine
Ion), substituted aryl sulfonate ions (eg
p-Toluenesulfonate ion, p-chlorobenzenes
Sulfonic acid ions), aryl disulfonic acid ions (for example,
1,3-benzenesulfonate ion, 1,5-naphtha
Range sulfonate ion, 2,6-naphthalenedisulfone
Acid ions), alkyl sulfate ions (eg methyl sulfate)
Ion), sulfate ion, thiocyanate ion, perchloric acid
Ion, tetrafluoroborate ion, picrate ion
, Acetate ion, trifluoromethanesulfonate ion
Is mentioned. In addition, ionic polymers or pigments and
Other dyes having a reverse charge may be used. Preferred yang
ON is sodium ion, potassium ion, triethyl
Ruammonium ion, tetraethylammonium ion
, Pyridinium ion, ethyl pyridinium ion,
Methylpyridinium ion, sodium,
Potassium, triethylammonium, pyridinium, N
-Ethylpyridinium is preferred. The preferred anion is
Perchlorate ion, iodide ion, bromide ion, substitution
Aryl sulfonate ions (eg p-toluene sulfone)
Acid ion). It is especially preferred to be a cation
Yes. m is a number greater than or equal to zero required to balance the charge
And 0 when forming an inner salt. Preferably 0
The number is 4 or more and more preferably 0, 1, 2 or less.
Or 3. D is a group necessary for forming a methine dye.
Yes, any methine dye can be formed by D
Preferably cyanine dye, merocyanine color
Elemental, rhodacyanine dye, trinuclear merocyanine dye, tetranuclear medicinal dye
Russianine dye, allopolar dye, hemicyanine color
Element, styryl dye, and the like. Details of these dyes
For details, see “Heterocyclic Compounds-” by F.M.Hamer.
Cyanine Dyes and Related Compounds '', John Wiley &
 Sons-New York, London, 1964, D.
M. Sturmer, “Heterocyclic Compounds-Special topics
 in cyclicchemistry ", Chapter 18, Section 14,
Pages 482-515, John Willie and Sun
(John Wiley & Sons)-New York, London,
1977, etc. Of the preferred dye
As a general formula, US Pat. No. 5,994,051 No. 3
General formulas described in columns 2-36, and 5,747,23
General formulas described in No. 6 columns 30 to 34 can be mentioned. Also,
Of cyanine dye, merocyanine dye, rhodacyanine dye
The general formula is U.S. Pat. No. 5,340,694 21-2.
Those shown in column 2 (XI), (XII), (XIII)
(However, n<sub>12</sub>, N<sub>15</sub>, N<sub>17</sub>, N<sub>18</sub>The number of is not limited, 0
The above integer (preferably 4 or less) is preferable. By D
More preferably, the methine dye formed is shear.
Nin pigments and merocyanine pigments.
In combination with the compound of general formula (II)
Indicates performance. In addition, the methine dye formed by D
Particularly preferred are cyanine dyes.
Excellent photographic properties when used in combination with compounds of general formula (II)
Show performance. It should be noted that the general formulas (Ia), (Ib), and
In (Ic), a cyanine dye is formed by D
Each case is expressed by a resonance formula such as the following general formula
It is also possible. [0058] Embedded image General formulas (Ia), (Ib) and (Ic)
In which D is preferably the above-mentioned D<sup>1</sup> Or the following D
<sup>a</sup>, D<sup>b</sup>Or D<sup>c</sup>It is a case where it represents. Of these
And more preferably D<sup>1</sup> , D<sup>a</sup>And such a place
In combination with the compound of general formula (II)
Indicates performance. Particularly preferably D<sup>1</sup> And such a place
Excellent photographic properties when used in combination with compounds of general formula (II)
Show performance. Most preferably, D<sup>1</sup> D above<sup>2</sup> Choose from
In such a case, the compound of general formula (II)
Excellent photographic performance when used in combination with objects. [0060] Embedded image D<sup>a</sup>Medium, L<sup>81</sup>And L<sup>82</sup>Each has a methine group
Represent. n<sup>8</sup>Represents 0, 1, 2, 3 or 4. Y<sup>81</sup>Is acid
Necessary for forming a sex nucleus or an acyclic acidic end group
Represents an atomic group. However, even if these rings are condensed, they are substituted.
It may have a group. [0062] Embedded image D<sup>b</sup>Medium, L<sup>91</sup>, L<sup>92</sup>, L<sup>93</sup>, L<sup>94</sup>, L<sup>95</sup>,
L<sup>96</sup>And L<sup>97</sup>Each represents a methine group. p<sup>9</sup>Is 0 or
1 is represented. n<sup>91</sup>And n<sup>92</sup>Is 0, 1, 2, 3 or
4 is represented. Y<sup>91</sup>And Y<sup>92</sup>Each form a nitrogen-containing heterocycle
Represents a group of atoms necessary for the
May also have a substituent. R<sup>91</sup>And R<sup>92</sup>Each
Substituted or unsubstituted alkyl, aryl, or
Represents a heterocyclic group. [0064] Embedded image D<sup>c</sup>Medium, L<sup>101</sup>, L<sup>102</sup>, L<sup>103</sup>, L<sup>104</sup>, L
<sup>105</sup>, L<sup>106</sup>And L<sup>107</sup>Represents a methine group. p<sup>Ten</sup>Is 0
Or 1 is represented. n<sup>101</sup>And n<sup>102</sup>Is 0, 1, 2, 3 or
Represents 4. Y<sup>101</sup>And Y<sup>102</sup>Forms a nitrogen-containing heterocycle
Represents a group of atoms necessary for the
May also have a substituent. R<sup>101</sup>And R<sup>102</sup>Is replaced
Or an unsubstituted alkyl group, aryl group, or compound
Represents a unicyclic group. Z<sup>11</sup>, Y<sup>92</sup>And Y<sup>102</sup>Nitrogen represented by
The heterocycle is preferably a 5- to 6-membered nitrogen-containing heterocycle.
And other rings (eg aromatic or non-aromatic carbon
A ring or a heterocyclic ring (specifically, V described above)
The ) May be condensed. Preferred as a condensed ring
Preferably 5-6 membered aromatic or non-aromatic carbocycle or
A heterocyclic ring, more preferably a benzene ring
Ring, naphthalene ring, etc.
Of the offene ring, etc.
A benzene ring is more preferable. Z<sup>11</sup>, Y
<sup>92</sup>And Y<sup>102</sup>The nitrogen-containing heterocycle formed by
Are thiazoline ring, thiazole ring, benzothiazole
Ring, oxazoline ring, oxazole ring, benzoxazo
Ring, selenazoline ring, selenazole ring, benzosele
Nazole ring, tellurazoline ring, tellurazole ring, benzo
Tellurazole ring, 3,3-dialkylindolenine ring
(Eg 3,3-dimethylindolenine), imidazole
Ring, imidazole ring, benzimidazole ring,
Xazole ring, isothiazole ring, pyrazole ring, 2-
Pyridine ring, 4-pyridine ring, 2-quinoline ring, 4-ki
Norin ring, 1-isoquinoline ring, 3-isoquinoline ring,
Imidazo [4,5-b] quinoxaline ring, oxadiazo
Ring, thiadiazole ring, tetrazole ring, pyrimid
And the above-mentioned ring condensed with a benzene ring.
I can make it. More preferably benzoxazole
Ring, benzothiazole ring, benzimidazole ring and
A quinoline ring, more preferably a benzoxazol
Ring and benzothiazole ring. In these V
Each substituent represented may be substituted. As a specific example
US Pat. No. 5,340,694, columns 23-24.
Z<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>, Z<sub>14</sub>And Z<sub>16</sub>As an example
The thing similar to what is being mentioned is mentioned. Y<sup>81</sup>Forms an acyclic or cyclic acidic nucleus
Represents the group of atoms needed to
It can also take the form of an acidic nucleus of an anine pigment. preferable
Y in shape<sup>81</sup>Next to the methine chain linking position
Or a carbonyl group. Acidity here
The nucleus is, for example, `` The Theory of the Photo '' edited by T.H.James.
graphic Process "4th edition, MacMillan Publishing
Published, 1977, page 198. Specifically
U.S. Pat. Nos. 3,567,719 and 3,57.
5,869, 3,804,634, 3,8
37,862, 4,002,480, 4,
925,777, JP-A-3-167546, etc.
There are listed. Acid nucleus is carbon, nitrogen
And chalcogens (typically oxygen, sulfur, selenium and
And 6-membered nitrogen-containing heterocycles composed of atoms)
Preferably, the following nuclei are mentioned. 2-pyrazolin-5-one, pyrazolidine
-3,5-dione, imidazolin-5-one, hydanto
In, 2 or 4-thiohydantoin, 2-iminooki
Sazolidin-4-one, 2-oxazolin-5-one,
2-thiooxazoline-2,4-dione, isoxazo
Phosphorus-5-one, 2-thiazoline-4-one, thiazoli
Gin-4-one, thiazolidine-2,4-dione, rho
Danine, thiazolidine-2,4-dithione, isoloader
Nin, indane-1,3-dione, thiophene-3-o
Thiophen-3-one-1,1-dioxide, in
Dolin-2-one, indoline-3-one, 2-oxo
Indazolinium, 3-oxoindazolinium, 5,
7-dioxo-6,7-dihydrothiazolo [3,2-
a] pyrimidine, cyclohexane-1,3-dione,
3,4-dihydroisoquinolin-4-one, 1,3-di
Oxane-4,6-dione, barbituric acid, 2-thio
Barbituric acid, chroman-2,4-dione, indazo
Rin-2-one, pyrido [1,2-a] pyrimidine-
1,3-dione, pyrazolo [1,5-b] quinazolone,
Pyrazolo [1,5-a] benzimidazole, pyrazolo
Pyridone, 1,2,3,4-tetrahydroquinoline-
2,4-dione, 3-oxo-2,3-dihydrobenzo
[D] Thiophene-1,1-dioxide, 3-dicyano
Methylene-2,3-dihydrobenzo [d] thiophene-
1,1-dioxide nuclei, and these nuclei forming
Carbonyl group or thiocarbonyl group
Active methylenes with structures such as len and cyanomethylene
Exomethylene structure substituted at the active methylene position of a compound
And nuclei that have been repeated. Y⁸¹Preferably hydantoin, 2 or
4-thiohydantoin, 2-oxazoline-5-o
, 2-thiooxazoline-2,4-dione, thiazoli
Gin-2,4-dione, rhodanine, thiazolidine-
2,4-dithione, barbituric acid, 2-thiobarbit
Oxalic acid, more preferably hydantoin, 2 or
4-thiohydantoin, 2-oxazoline-5-o
, Rhodanine, barbituric acid, 2-thiobarbitu
Luric acid. Particularly preferably 2 or 4-thiohydanto
In, 2-oxazolin-5-one, rhodanine
Most preferred is rhodanine. Y⁹¹And Y¹⁰¹Nitrogen formed by
As an elementary heterocycle, preferably a 5- to 6-membered nitrogen-containing heterocycle
Yes, more preferably Y⁸¹A heterocycle represented by
From which an oxo group or a thioxo group is removed. The
More preferably hydantoin, 2 or 4-thiohydan
Toin, 2-oxazolin-5-one, 2-thiooxa
Zolin-2,4-dione, thiazolidine-2,4-dio
, Rhodanine, thiazolidine-2,4-dithione,
Rubituric acid, 2-thiobarbituric acid to oxo group,
Or a thioxo group is removed, more preferably
Are hydantoin, 2 or 4-thiohydantoin, 2
-Oxazolin-5-one, rhodanine, barbitur
Acid, 2-thiobarbituric acid to oxo group, or thio
Excluding the xo group, particularly preferably 2 or 4
-Thiohydantoin, 2-oxazolin-5-one,
-Danine minus oxo and thioxo groups
Yes, most preferably the thioxo group is removed from rhodanine
It is a thing. R¹², R^{twenty two}, R⁹¹, R⁹², R¹⁰¹, R¹⁰²Oh
And acidic nucleus Y⁸¹A substituent on the nitrogen atom (if any
R⁸¹Are substituted or unsubstituted, alkyl
Represents an alkyl group, an aryl group, or a heterocyclic group, and has the general formula (I)
The groups listed as examples of R in methine dyes are preferred.
Yes. R¹², R^{twenty two}, R⁸¹, R⁹¹, R⁹², R¹⁰¹, R¹⁰²Hako
Of these, substituted or unsubstituted alkyl groups are preferred.
It is more preferable that the acid group is a substituted alkyl group.
Yes. Specifically, the acid described as a preferred example in R above
And the same as the alkyl group substituted by the group
Those are preferred. L¹¹, L¹², L¹³, L¹⁴, L¹⁵, L^{twenty one}, L
^{twenty two}, L^{twenty three}, L⁸¹, L⁸², L⁹¹, L⁹², L⁹³, L⁹⁴,
L⁹⁵, L⁹⁶, L⁹⁷, L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, L
¹⁰⁵, L¹⁰⁶And L¹⁰⁷Each independently represents a methine group.
The These methine groups may have a substituent.
Examples of the substituent include each substituent represented by V.
It may also form a ring with other methine groups, or
Z¹¹, Y⁸¹, Y⁹¹, Y⁹², Y¹⁰¹, Y¹⁰², R, R¹², R
^{twenty two}, R⁹¹, R⁹², R¹⁰¹ , R¹⁰² To form a ring with
You can also. L¹⁴, L¹⁵, L⁹⁶, L⁹⁷, L¹⁰⁶And L
¹⁰⁷As preferred, it is an unsubstituted methine group. N¹ , N² , N⁸, N⁹¹, N⁹², N¹⁰¹And
N¹⁰²Represents 0, 1, 2, 3 or 4 and is 2 or more
Repeats the methine group but need not be identical. n
¹ , N² , N⁸, N⁹¹And n¹⁰²Preferably 0,
1, 2, 3, more preferably 0, 1, 2
Particularly preferably 0 or 1, most preferably
0. n⁹²And n¹⁰¹Preferably 0 or
1, more preferably 0. n¹ Is 0
If L¹¹Is preferably an unsubstituted methine group, n
¹ L is 1¹²Is substituted with an unsubstituted alkyl group
Methine group, L¹¹, L¹³Each is an unsubstituted methine group.
Are preferred. L¹²In particular a methyl-substituted methine group or
It is preferably a til-substituted methine group, and further ethyl
It is preferably a substituted methine group. n²When is 0
L^{twenty one}Is preferably an unsubstituted methine group, n²
L is 1^{twenty two}Substituted with an unsubstituted alkyl group
Methine group, L^{twenty one}, L^{twenty three}Each must be an unsubstituted methine group
Is preferred. L^{twenty two}In particular a methyl-substituted methine group or ethyl
It is preferably a substituted methine group.
A substituted methine group is preferred. P¹ , P⁹ And p^TenAre independently 0
Or 1 is represented. Preferably it is 0. X^{twenty two}Is a sulfur atom, oxygen atom, selenium source
Child, tellurium atom, nitrogen atom (N-V^e) Or carbon atoms
(CV^fV^g). Where V^e, V^f, V^gIs hydrogen
An atom, or a substituent (eg, V described above), but preferred
Or a hydrogen atom, an alkyl group, an aryl group, or a
It is a cyclic group. An alkyl group, an aryl group, or a heterocyclic group;
The same thing as R mentioned above is mentioned, The same thing is mentioned.
preferable. Particularly preferred is an alkyl group. X^{twenty two}When
And preferably a sulfur atom, an oxygen atom, a selenium atom,
Is a nitrogen atom, more preferably a sulfur atom, oxygen
Atom or selenium atom, particularly preferably sulfur atom
It is a child or an oxygen atom. General formula (Ia), (Ib) or (Ic)
D is D¹ Or D² And R and R
¹², And R and R^{twenty two}As an alkyl group substituted with an acid group,
Some cases are preferred. In addition, R and R¹², And R and R^{twenty two}
Preferably, the combination of R and R¹²Any one of
Is an alkyl group substituted with a sulfo group, and the other is
When the acid group other than the sulfo group is a substituted alkyl group,
And R and R^{twenty two}Any one of the above is substituted with a sulfo group
The other is an acid group other than the sulfo group.
This is the case when it is an alkyl group. Alkyl substituted with an acid group
Examples of the ru group include those described in the above R.
Are preferred. More preferably, the alkyl having a sulfo group is used.
3-sulfopropyl group, 4-sulfobutyl group
Group, 3-sulfobutyl group, 2-sulfoethyl group
Yes, more preferably in the case of 3-sulfopropyl group
Yes, and an alkyl group having an acid group other than a sulfo group
Carboxymethyl group, methanesulfonylcarbamoy
This is the case for the rumethyl group. V^{twenty one}, V^{twenty two}, V^{twenty three}, V^{twenty four}Are each a hydrogen atom or
Represents a substituent, and each substituent represented by the above V is represented as a substituent.
The two adjacent substituents are linked to each other.
To form a saturated or unsaturated condensed ring.
Or aromatic groups (eg phenyl), and aromatic hetero
It is not a cyclic group (for example, 1-pyrrolyl). This
Una V^{twenty one}, V^{twenty two}, V^{twenty three}, V^{twenty four}Especially good photographic properties
Show performance. In addition, as a substituent, except these,
But it ’s okay, V^{twenty one}, V^{twenty four}Both must be hydrogen atoms
Is preferred, V^{twenty two}, V^{twenty three}Are each a hydrogen atom or an alkyl group
(Eg methyl), alkylthio groups (eg methylthio)
E), a cyano group, or a halogen atom (eg, fluorine, salt)
Elemental, bromine, iodine). In addition,
V^{twenty two}, V^{twenty three}Is preferred if both are alkoxy groups
It ’s not. In addition, V^{twenty two}, V^{twenty three}Of which, V^{twenty three}Is more preferred
Is a hydrogen atom and V^{twenty two}Is more preferably an alkyl group
(For example, methyl), an alkoxy group (for example, methoxy),
Or a halogen atom, more preferably a halogen atom
Particularly preferably a chlorine atom or a bromine atom.
Most preferably, it is a chlorine atom. General formulas (Ia), (Ib) and (Ic)
More preferably, D is D as defined above.^Three Or D
^Four It is a case where it represents. D^Three , And D^Four In addition,
Preferably D^Three It is. In such cases, the general formula (I
Shows particularly excellent photographic performance when used in combination with compound (I). D^Three
 Medium, R³²Represents an alkyl group substituted with an acid group. R and R
³²If both are alkyl groups substituted by acid groups,
Preferably R and R³²As a combination of
Preferably R and R³²Any one of the
And the other is an acid group other than a sulfo group.
This is a case of a substituted alkyl group. Acid group substituted
Examples of the alkyl group include those described above for R.
Similar ones are preferred. More preferably, a sulfo group
As an alkyl group having a 3-sulfopropyl group, 4-
Sulfobutyl group, 3-sulfobutyl group, 2-sulfoethyl
Group, more preferably 3-sulfopropyl.
In addition, an amine having an acid group other than a sulfo group.
As alkyl groups, carboxymethyl group, methanesulfonate
This is the case for a rucarbamoylmethyl group. X³²Represents a sulfur atom or an oxygen atom.
Preferably it is a sulfur atom. V³²Is a halogen atom (eg
Fluorine, chlorine, bromine, iodine), more preferably
Is a chlorine atom or a bromine atom, particularly preferably chlorine
Is an atom. D^Four Medium, R⁴²Is an alkyl group substituted by an acid group
Represents. R and R⁴²Both have an acid group substituted
Preferred is a kill group, and further R and R⁴²Set of
Preferably, R and R are combined³²Either one of the
An alkyl group substituted with a rupho group, and the other is sulfo
This is a case where the acid group other than the group is a substituted alkyl group.
  The alkyl group substituted with an acid group is described in the above R.
The same thing is preferable. More preferred
Alternatively, as an alkyl group having a sulfo group, 3-sulfo
Propyl group, 4-sulfobutyl group, 3-sulfobutyl
Group, 2-sulfoethyl group, more preferably
Is the case of 3-sulfopropyl group, and sulfo group
Carboxymethyl as an alkyl group with an acid group other than
Group, methanesulfonylcarbamoylmethyl group
The X⁴²Represents a sulfur atom or an oxygen atom.
It is preferably an oxygen atom. V⁴²Is a halogen atom (eg
Fluorine, chlorine, bromine, iodine), more preferably
Is a chlorine atom or a bromine atom, particularly preferably chlorine
Is an atom. General formula (Ia), (Ib) or (Ic)
When using together with general formula (II)
If the mutual spectral sensitivity maximum wavelength is within 100 nm,
More preferably within 70 nm, especially preferred
Or within 50 nm, more preferably within 40 nm.
That's right. Structurally, the general formulas (Ia), (Ib),
When using a preferred cyanine dye as (Ic),
Preferred combinations include those represented by the general formulas (Ia) and (I
b) or (Ic) has three methine chains and has the general formula
(II) is the case where the number of methine chains is three, or the general formula
The number of methine chains in (Ia), (Ib), or (Ic) is 1
The number of methine chains of general formula (II) is one.
The Furthermore, the general formula (Ia), (Ib) or (Ic)
When the number of methine chains in general formula (II) is three, general formula (I
a), (Ib), or (Ic) is a benzothiazole nucleus
In the case of having a benzoxazole nucleus, the general formula (II) is
It has two nzothiazole nuclei and has the general formulas (Ia) and (I
b) or (Ic) has two benzoxazole nuclei
In general, formula (II) has two benzoxazole nuclei
It is preferable. Formula (Ia), (Ib), or
When the number of methine chains of (Ic) and general formula (II) is one,
The general formula (Ia), (Ib) or (Ic) is benzothiazo
In the case of having two nuclei, general formula (II) is benzothiazo
It is preferable to have two kernels. Next, together with the methine dye of the general formula (I)
About cyanine dyes represented by the general formula (II) used
Will be described in detail. In the general formula (II), Z³¹, Z³²Represented by
As the nitrogen-containing heterocycle, preferably 5 to 6-membered nitrogen-containing
Heterocycles, and other rings (eg, aromatic or non-aromatic)
Aromatic carbocycle or heterocycle (specifically, V or the like mentioned above)
Can be mentioned. ) May be condensed. Condensed ring
Preferably, it is a 5- to 6-membered aromatic carbocycle.
More preferred are a benzene ring and a naphthalene ring, especially
A benzene ring is preferred. Represented by general formula (II)
The compound has the general formula (Ia), (Ib), or (Ic)
Excluding the compound represented by Z³¹, Z³²Represented by
The nitrogen-containing heterocycle represented by the general formula (Ia), (Ib), or
The substitution of two alkoxy groups as in (Ic)
Absent. Z³¹, Z³²Is preferably a thiazoline ring, thiazo
Ring, benzothiazole ring, oxazoline ring, oxa
Sol ring, benzoxazole ring, selenazoline ring,
Lenazole ring, benzoselenazole ring, tellrazoline
Ring, tellurazole ring, benzotelrazole ring, 3,3-
Dialkylindolenine rings (eg 3,3-dimethyli
Ndrenine), imidazoline ring, imidazole ring, ben
Diimidazole ring, isoxazole ring, isothiazole
Ring, pyrazole ring, 2-pyridine ring, 4-pyridine
Ring, 2-quinoline ring, 4-quinoline ring, 1-isoquinoline
Ring, 3-isoquinoline ring, imidazo [4,5-b] key
Noxalin ring, oxadiazole ring, thiadiazole
Rings, tetrazole rings, pyrimidine rings, and these rings
Condensed with benzene ring, naphthalene ring or other carbon ring
Can be mentioned. More preferably benzoxazo
Ring, benzothiazole ring, benzimidazole ring
And a quinoline ring, more preferably benzoxa
Zole ring and benzothiazole ring. These mentioned above
Each substituent represented by V may be substituted. Specific examples and
US Pat. No. 5,340,694 Nos. 23-24
Z in column₁₁, Z₁₂, Z₁₃, Z₁₄And Z₁₆Take as an example
The thing similar to what is mentioned is mentioned. R³¹, R³²An alkyl group represented by
Examples of the group and heterocyclic group include the groups described for R above.
In addition, a substituted or unsubstituted alkyl group
In which at least one of them is substituted with an acid group.
It is preferably an alkyl group, and both of them are acid groups.
A substituted alkyl group is preferred. In particular
An acid group substituted with an acid group described as a preferred example in R above.
The same thing as the rualkyl group is mentioned, and the same thing is preferable.
Yes. In addition, R³¹And R³²As a combination of
In general formula (Ia), (Ib), or (Ic), D
Is D¹Or D²And R and R¹², And R and R
^{twenty two}The same as described as a preferable example of the combination of
Like, R³¹And R³²Any one of was substituted with a sulfo group
An alkyl group and the other is an acid group other than a sulfo group.
Preferred is a substituted alkyl group. Place with sulfo group
Substituted alkyl groups and acid groups other than sulfo groups
Examples of the alkyl group include those described above for R.
Similar ones are preferred. More preferably, the alkyl having a sulfo group is used.
3-sulfopropyl group, 4-sulfobutyl group
Group, 3-sulfobutyl group, 2-sulfoethyl group
Yes, more preferably in the case of 3-sulfopropyl group
Yes, and an alkyl group having an acid group other than a sulfo group
Carboxymethyl group, methanesulfonylcarbamoy
This is the case for the rumethyl group. L³¹, L³², L³³, L³⁴, L³⁵, L³⁶, L
³⁷The methine group represented by may be unsubstituted or substituted
Well, examples of the substituent include the substituents represented by V.
It is done. L³¹, L³², L³⁶, L³⁷Is preferably unsubstituted
It is a chin group. N^ThreeRepresents 0, 1, 2, 3 or 4 and 2
In these cases, the methine group is repeated, but it must be the same.
Absent. Preferably 0, 1, 2, 3 and more preferably
Is 0, 1, 2 or more preferably 0 or 1.
Particularly preferred is 0. n^Three L is 0, L
³³Is preferably an unsubstituted methine group, n^Three Is 1
If yes, L³⁴Is a methine substituted with an unsubstituted alkyl group
Group, L³³, L³⁵Is preferably an unsubstituted methine group
Yes. L³⁴In particular methyl-substituted methine groups or ethyl-substituted meth
It is preferably a tin group, and further ethyl-substituted methine
It is preferably a group. p³¹, P³²Represents 0 or 1
And preferably 0. M^ThreeAs each ion explained in M above
Especially preferred are cations
Yes. Preferred cations are sodium, potassium, trie.
Til ammonium, pyridinium, N-ethylpyridini
It is a um. m^ThreeIs necessary to neutralize the charge in the molecule.
Represents the required number of 0 or more, 0 when forming an inner salt
is there. Preferably it is 0, 1, 2 or 3. The methine dye represented by the general formula (II) is further
Is preferably represented by the general formula (IIa). General
X in the formula (IIa)⁴¹, X⁴²Is a sulfur atom, oxygen source
Child, selenium atom, tellurium atom, nitrogen atom (N-V^h),
Or carbon atom (CVⁱV^j). Where V^h, V
ⁱ, V^jIs a hydrogen atom or a substituent (for example, V described above)
Preferably, a hydrogen atom, an alkyl group, an aryl
Or a heterocyclic group. An alkyl group, an aryl group,
Alternatively, examples of the heterocyclic group include those similar to R described later.
Similar ones are preferred. Particularly preferably, alkyl
It is a group. X⁴¹, X⁴²Preferably, a sulfur atom, an acid
Elementary atom, selenium atom or nitrogen atom, more preferred
Or a sulfur atom, an oxygen atom, or a selenium atom,
Particularly preferred is a sulfur atom or an oxygen atom. In addition,
X⁴¹, X⁴²Is not preferred when both are oxygen atoms.
X⁴¹, X⁴²Most preferably both are fields of sulfur atoms
In such cases, particularly good photographic performance is exhibited.
The R⁴¹, R⁴²An alkyl group represented by
Examples of the group and heterocyclic group include the groups described for R above.
R of general formula (II)³¹, R³²Similar to
And similar combinations are preferred. V⁴¹, V⁴², V⁴³, V⁴⁴, V⁴⁵, V⁴⁶, V
⁴⁷, V⁴⁸As the substituent represented by each of the above,
A substituent, and two adjacent substituents are linked together
To form a saturated or unsaturated condensed ring.
The ring is preferably a carbocyclic ring. That
Such saturated or unsaturated carbocycles include, for example, ben
List zen, cyclohexene and naphthalene rings
However, it is preferable not to form a condensed ring.
V⁴¹, V⁴⁴, V⁴⁵, V⁴⁸Are both hydrogen atoms
Is preferred, V⁴², V ⁴³, V⁴⁶, V⁴⁷Are each a hydrogen atom
Or an alkyl group (for example, methyl), an aryl group (for example,
Phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl),
Alkoxy groups (eg methoxy), alkylthio groups (eg
Methylthio), cyano group, or halogen atom (eg
Fluorine, chlorine, bromine, iodine)
Yes. More preferably V⁴³, V⁴⁷Are both hydrogen atoms,
V⁴², V⁴⁶Are both halogen atoms (preferably chlorine or odor
Element), more preferably a chlorine atom. L⁴¹, L⁴², L⁴³There is no methine group represented by
May be substituted or substituted, and the substituent is V
Each substituent represented is mentioned. N^FourRepresents 0, 1, 2, 3 or 4 and 2
In these cases, the methine group is repeated, but it must be the same.
Absent. Preferably 0, 1, 2, 3 and more preferably
Is 0, 1, 2 or more preferably 0 or 1.
Particularly preferred is 0. n^FourL is 0, L
⁴¹Is preferably an unsubstituted methine group, n^FourIs 1
If yes, L⁴²Is a methine substituted with an unsubstituted alkyl group
Group, L⁴¹, L⁴³Is preferably an unsubstituted methine group
Yes. L⁴²In particular methyl-substituted methine groups or ethyl-substituted meth
It is preferably a tin group, and further ethyl-substituted methine
It is preferably a group. M^FourAs each ion explained in M above
Especially preferred are cations
Yes. Preferred cations are sodium, potassium, trie.
Til ammonium, pyridinium, N-ethylpyridini
It is a um. m^FourIs necessary to neutralize the charge in the molecule.
Represents the required number of 0 or more, 0 when forming an inner salt
is there. Preferably it is 0, 1, 2 or 3. The methine dye represented by the general formula (IIa) is
Furthermore, when used in a green to red sensitive emulsion, the general formula (II
I) When used in a blue-sensitive emulsion, it is expressed in the form of (IV)
It is preferred that Of the general formulas (III) and (IV),
Preferred is general formula (IV), and in such a case, in particular
Excellent photographic performance. The following are the dyes represented by the general formula (III).
And will be described in detail. X in the general formula (III)⁵¹, X⁵²
Represents oxygen or sulfur atom, but is used in green sensitive emulsion
X is preferably X⁵¹Is oxygen atom or sulfur source
Child, X⁵²Is the case of an oxygen atom, more preferably
X⁵¹, X⁵²Are both oxygen atoms, in red sensitive emulsion
When used in X, preferably X⁵¹Is oxygen atom or sulfur
Yellow atom, X⁵²Is the case of a sulfur atom, more preferably
Is X⁵¹, X⁵²Are both sulfur atoms. R⁵¹, R⁵², R⁵³An alkyl group represented by
As the aryl group and heterocyclic group, each group described in the above R
R⁵¹, R⁵²As general formula (I
I) R³¹, R³²And similar combinations
Is preferred. R⁵³Is preferably an unsubstituted alkyl group
Particularly preferably a methyl group or an ethyl group.
Yes. V⁵¹, V⁵², V⁵³, V⁵⁴, V⁵⁵, V⁵⁶In the table
Examples of the substituents include the substituents represented by V.
Two adjacent substituents are linked together and saturated
Or an unsaturated condensed ring is not formed. V⁵¹, V
⁵³, V⁵⁴, V⁵⁶Is preferably a hydrogen atom,
V⁵², V⁵⁵Is an alkyl group (eg methyl), an aryl group
(For example, phenyl), an aromatic heterocyclic group (for example, 1-pyro
Yl), alkoxy groups (eg methoxy), alkylthio
O group (eg methylthio), cyano group, or halogen atom
Be a child (eg fluorine, chlorine, bromine, iodine)
Preferred is a halogen atom, particularly preferred.
Preferably a chlorine atom or a bromine atom, most preferably
Is a chlorine atom. M^FiveAs each ion explained in M above
Especially preferred are cations
Yes. Preferred cations are sodium, potassium, trie.
Til ammonium, pyridinium, N-ethylpyridini
It is a um. m^FiveIs necessary to neutralize the charge in the molecule.
Represents the required number of 0 or more, 0 when forming an inner salt
is there. Preferably it is 0, 1, 2 or 3. The following are the dyes represented by the general formula (IV).
Will be described in detail. X in the general formula (IV)⁶¹Is oxygen field
Represents a sulfur atom, but a sulfur atom is particularly preferred.
That's right. R⁶¹, R⁶²An alkyl group represented by
Examples of the group and heterocyclic group include the groups described for R above.
R⁵¹, R⁵²As R of general formula (II)
³¹, R³²The same and similar combinations are preferred
Yes. V⁶¹, V⁶², V⁶³, V⁶⁴, V⁶⁵, V⁶⁶In the table
Examples of the substituents include the substituents represented by V.
Two adjacent substituents are linked together and saturated
Or an unsaturated condensed ring is not formed. V⁶¹, V
⁶³, V⁶⁴, V⁶⁶Is preferably a hydrogen atom,
V⁶², V⁶⁵Is an alkyl group (eg methyl), an aryl group
(For example, phenyl), an aromatic heterocyclic group (for example, 1-pyro
Yl), alkoxy groups (eg methoxy), alkylthio
O group (eg methylthio), cyano group, or halogen atom
Be a child (eg fluorine, chlorine, bromine, iodine)
Preferred is a halogen atom, particularly preferred.
Preferably a chlorine atom or a bromine atom, most preferably
Is a chlorine atom. M⁶As each ion explained in M above
Especially preferred are cations
Yes. Preferred cations are sodium, potassium, trie.
Til ammonium, pyridinium, N-ethylpyridini
It is a um. m⁶Is necessary to neutralize the charge in the molecule.
Represents the required number of 0 or more, 0 when forming an inner salt
is there. Preferably it is 0, 1, 2 or 3. Preferred in the silver halide emulsion of the present invention
A compound of general formula (Ia), (Ib) or (Ic)
And combinations of compounds of general formula (II) are described below.
The When used in a red sensitive emulsion layer, the general formula
The compound of (II) is represented by the general formula (III), and X⁵¹And X⁵²
Are both sulfur atoms and R⁵¹And R⁵²Is sulfoalkyl
Group, carboxyalkyl group or alkylsulfonyl group
Rubamoylalkyl group, R⁵³Is a methyl group or
Til group and V⁵¹, V⁵³, V⁵⁴, V⁵⁶Is a hydrogen atom
V⁵², V⁵⁵Is an alkyl group (eg methyl), alcohol
A xyl group (eg methoxy), an alkylthio group (eg
Tilthio), a cyano group, or a halogen atom (eg, fluorine
Element, chlorine, bromine, iodine), more preferably a halogen source
A child, particularly preferably a chlorine atom, M^FiveIs organic or
An inorganic monovalent cation, m^FiveIs 0 or 1
It is preferable. The dye combined with this is represented by the general formula (I
a) or (Ib), where D is D^Four And Z¹And X
⁴²Is one oxygen atom, the other is a sulfur atom, and V¹ , V
² Is a hydrogen atom, Ra and Rb are methyl, R and
R⁴²Are each a sulfoalkyl group or a carboxyalkyl group.
Or an alkylsulfonylcarbamoylalkyl group.
V⁴²Is a halogen atom (eg, fluorine, chlorine, bromine,
Iodine), more preferably a chlorine atom, and M is organic or
Or an inorganic monovalent cation, and m is 0 or 1.
It is preferable. When used in a green sensitive emulsion layer, the general formula
The compound of (II) is represented by the general formula (III), and X⁵¹And X⁵²
Are both oxygen atoms and R⁵¹And R⁵²Are each sulfoal
Kill group, carboxyalkyl group or alkylsulfonyl
A rucarbamoylalkyl group, R⁵³Is a methyl group or
Is an ethyl group and V⁵¹, V⁵³, V⁵⁴, V⁵⁶Is a hydrogen atom
And V⁵², V⁵⁵Is an alkyl group (eg methyl),
A reel group (for example, phenyl), an aromatic heterocyclic group (for example,
2-thienyl), alkoxy group (eg methoxy), a
Alkylthio group (for example, methylthio), cyano group, or
Rogen atoms (eg fluorine, chlorine, bromine, iodine)
More preferably, it is a halogen atom, and M^FiveIs organic or nothing
The monovalent cation of the machine, m^FiveIs 0 or 1
Are preferred. The dye combined with this is represented by the general formula (I
a) or (Ib), where D is D^Four And Z¹And X
⁴²Is one oxygen atom, the other is a sulfur atom, or both oxygen
An atom, more preferably Z¹And X⁴²Both oxygen
Atomic and V¹ , V² Is a hydrogen atom, Ra and Rb
Is methyl, R and R⁴²Is a sulfoalkyl group, carbo
Xylalkyl group or alkylsulfonylcarbamoyl
An alkyl group, V⁴²Is a halogen atom (eg
Element, chlorine, bromine, iodine), more preferably a chlorine atom
Yes, M²Is an organic or inorganic monovalent cation,
m²Is preferably 0 or 1. When used in a blue-sensitive emulsion layer, the general formula
The compound of (II) is represented by the general formula (IV), and X⁶¹Is a sulfur field
Child and R⁶¹And R⁶²Are each a sulfoalkyl group, carbo
Xylalkyl group or alkylsulfonylcarbamoyl
An alkyl group, V⁶¹, V⁶³, V⁶⁴, V⁶⁶Are both
A hydrogen atom, V⁶², V⁶⁵Are each an alkyl group (e.g.
Methyl), aryl groups (eg phenyl), aromatic hetero
A cyclic group (eg 1-pyrrolyl), an alkoxy group (eg
Toxi), alkylthio group (eg methylthio), cyan
Group or a halogen atom (for example, fluorine, chlorine, bromine,
Iodine), more preferably halogen atoms, particularly preferably
Is a chlorine atom, M⁶Is an organic or inorganic monovalent cation
Is on and m⁶Is preferably 0 or 1.
The dye combined with this is represented by (Ia) or (Ib).
D is D^Three And Z¹And X³²Are both sulfur atoms
V¹ , V² Is a hydrogen atom and Ra and Rb are methyl
R and R³²Is sulfoalkyl group, carboxyal
Kill group or alkylsulfonylcarbamoylalkyl
V and V³²Is a halogen atom (eg fluorine, chlorine,
Bromine, iodine), more preferably a chlorine atom or
Bromine atom, M²Is an organic or inorganic monovalent cation
M²Is preferably 0 or 1. The general formulas (Ia) and (I
b) of the compound of (Ic) (including subordinate compounds)
A specific example is shown, but this is not intended to limit the present invention.
There is no. [0111] Embedded image [0112] Embedded image[0113] Embedded image [0114] Embedded image [0115] Embedded image [0116] Embedded image[0117] Embedded image [0118] Embedded image The compounds of the general formula (II) of the present invention (following
General formula (IIa), general formula (III), general formula (IV)
Specific examples of the compound (including the compound of
Is not limited. [0120] Embedded image[0121] Embedded image[0122] Embedded image [0123] Embedded image[0124] Embedded image The general formulas (Ia), (Ib), (I
c) and a compound represented by the general formula (II) (subordinate concept)
(Including compounds) by F.M.Hamer “Heterocyclic Compou
nds-Cyanine Dyes and Related Compounds ", John Wil
ey & Sons-New York, London, 1964
Published by D.M.Sturmer, `` Heterocyclic Compounds-Specialt
opics in cyclic chemistry ", Chapter 18, First
Section 4, pages 482-515, John Wiley & Sons
New York, London, 1977, “Rodd'sChemis
try of Carbon Compounds "2nd Ed. vol. IV, part B, 1
977, Chapter 15, Pages 369-422, Elsevier S
cience Publishing Company Inc., New York,
Can be synthesized based on the method described in the above. The general formula (Ia), (Ib) or
The compound of (Ic) and the compound of general formula (II) are in the same emulsion.
Even if one type is used each, two or more types are used.
May be. General formula (Ia), (Ib), or
In the same emulsion of the compound of (Ic) and the compound of general formula (II)
The ratio of the addition amount in is arbitrary, and the preferred addition molar ratio is
Depending on the purpose and purpose, preferably 1000/1 ~
1/1000, more preferably 100/1 to 1 /
100, more preferably 10/1 to 1/10
Yes, particularly preferably 5/1 to 1/5. The general formula (Ia), (Ib) or
The compound of (Ic) and the compound of general formula (II) are in the same emulsion.
In combination with other sensitizing dyes other than the present invention. Used
Preferably, the dye to be used is a cyanine dye, merocyanine
Dye, rhodacyanine dye, trinuclear merocyanine dye, 4
Nuclear merocyanine dye, allopolar dye, hemicyanine
Examples thereof include dyes and styryl dyes. More preferred
Is cyanine dye, merocyanine dye, rhodacyanine dye
Particularly preferred are cyanine dyes. these
For more information on dyes, see “Heterocyclic Co” by F.M.Hamer.
mpounds-Cyanine Dyes and Related Compounds ", John
 Wiley & Sons-New York, London, 1964
Annual publication by D.M.Sturmer, `` Heterocyclic Compounds-Specia
l topics in cyclic chemistry ", Chapter 18, Chapter
Verse 14, 482-515, John Willie Ann
John Wiley & Sons-New York, Russia
Ndon, 1977, etc. Further explanation will be given of RD17643.
23-24 pages, RD18716, page 648, right column-649
Page right column, RD308119 page 996 right column to page 998 right
Column, European Patent No. 0565096A1, page 65, 7-1.
It is preferable to use what is described in line 0.
Yes. Also, U.S. Pat. No. 5,747,236 (especially No.
30-39), US Pat. No. 5,340,694 (Special)
21 to 60, except that (XI), (XII), (XII
In the sensitizing dye shown in I), n₁₂, N₁₅, N₁₇, N
₁₈The number of is not limited and is an integer of 0 or more (preferably 4 or less)
And ), Shown in general formulas and specific examples
Sensitized dyes can also be preferably used. One kind of these sensitizing dyes that can be used in combination is used.
2 or more types may be used, and in the case of 2 or more types,
Particularly preferred are those having the effect of supersensitization, and their representatives
Examples are U.S. Pat. Nos. 2,688,545 and 2,973.
No. 7,229, No. 3,397,060, No. 3,5
22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No.
3,666,480, 3,672,898,
No. 3,679,428, No. 3,303,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
No. 7, British Patent No. 1,344,281, No. 1,50
7,803, JP-B 43-49336, 53-1.
2375, JP-A 52-110618, and 52-1.
No. 09925 and the like. Spectral sensitizing effect itself with sensitizing dye
Dyes that do not have visible light or substances that do not substantially absorb visible light
Include in the emulsion a substance that is high quality and exhibits supersensitization.
Yes. Strong intensity useful in spectral sensitization in the present invention
Color sensitizers (eg, pyrimidylamino compounds, triazis
Nylamino compounds, azolium compounds, aminostyryl
Compound, aromatic organic acid formaldehyde condensate, azai
Compounds, cadmium salts), and supersensitizers and sensitizers
Examples of combinations of dyes are U.S. Pat. No. 3,511,
No. 664, No. 3,615,613, No. 3,61
No. 5,632, No. 3,615,641, No. 4,5
96,767, 4,945,038, 4,
965,182, 4,965,182,
No. 2,933,390, No. 3,635,721, No.
No. 3,743,510, No. 617,295, No.
No. 3,635,721 etc., and its use
Regarding the law, the method described in the above patent is preferred.
Yes. Next, the silver halide photographic emulsion of the present invention and
The silver halide photographic light-sensitive material will be described in detail. Book
The general formula (Ia), (Ib), or (I
c) and methine dyes of the general formula (II) as sensitizing dyes
These methine dyes (ma
The same applies to other sensitizing dyes and supersensitizers).
The timing of addition to the silver halide emulsion of the present invention is not limited.
Any process of emulsion preparation that has been found to be useful in
It may be in the middle. For example, US Pat. No. 2,735,
No. 766, No. 3,628,960, No. 4,18
No. 3,756, No. 4,225,666, JP-A-58.
-184142, 60-196749, etc.
The silver halide grain formation step and / or
Or before desalting, during desalting process and / or after desalting
Until the start of chemical ripening, JP-A-58-113
As disclosed in No. 920 etc.
Or the emulsion at the time of the process, until the coating after chemical ripening
It is added in the process at any time before it is applied.
May be. Also, U.S. Pat. No. 4,225,666,
Same as disclosed in Kaisho 58-7629 etc.
Compound alone or in combination with compounds of different structure
For example, during the particle formation process and during the chemical ripening process
Divided into after the completion of academic aging, or before or during chemical aging
And may be divided and added, for example, divided into
Seeds of compound and compound combination to be added in portions
It may be added in various forms. The methine dye of the present invention (and other sensitization)
The same applies to dyes and supersensitizers)
Depending on the shape and size of the silver halide grains, either
May be added, but is preferred per mole of silver halide.
Or 1 × 10^-8~ 8x10 ^-1Mole, more preferably 1
× 10^-6~ 8x10^-3Can be used in moles. example
If the silver halide grain size is 0.2 to 1.3 μm
2 × 10 per mole of silver halide^-6~ 3.
5 × 10^-3Molar addition amount is preferred, 7.5 × 10^-6~
1.5 × 10^-3A molar addition amount is more preferable. The methine dye of the present invention (and other sensitization)
The same applies to dyes and supersensitizers).
Can be scattered. These are also suitable solvents,
For example, methyl alcohol, ethyl alcohol, methyl
Rosolve, acetone, water, pyridine or a mixture of these
Dissolved in a solvent and added to the emulsion in the form of a solution
You can also. At this time, bases, acids, surfactants, etc.
Additives can also coexist. Also ultrasonic to dissolve
Can also be used. Also, a method for adding this compound
As described in U.S. Pat. No. 3,469,987.
The compound is dissolved in a volatile organic solvent, and the solution
Is dispersed in a hydrophilic colloid, and this dispersion is added to the emulsion.
As described in Japanese Patent Publication No. 46-24185
When dispersed in a water-soluble solvent,
Method of addition, described in US Pat. No. 3,822,135
The compound is dissolved in a surfactant and the solution is emulsified.
A method of adding the solution into the inside, as described in JP-A-51-74624
Such as red-shifting compounds,
A method for adding a solution into an emulsion, JP-A-50-80826
To a substantially water-free acid as described in
The method of dissolving and adding the solution to the emulsion is used.
The In addition, U.S. Pat. No. 2,91
2,343, 3,342,605, 2,99
Those described in 6,287, 3,429,835, etc.
The method is also used. An organic solvent for dissolving the methine dye of the present invention;
For example, methyl alcohol, ethyl alcohol,
n-propanol, isopropanol, n-butanol,
Sobutanol, t-butanol, benzyl alcohol,
Fluorine alcohol, methyl cellosolve, acetone, pyridi
Or a mixed solvent thereof. Water, the above organic solvent, or a mixture thereof
When dissolving the methine dye of the present invention in a solvent, a base is used.
It is also preferable to add. Organic base, inorganic as base
Any base can be used, for example amine derivatives (eg tri
Ethylamine, triethanolamine), pyridine derivative
Body, sodium hydroxide, potassium hydroxide, sodium acetate
And potassium acetate. Preferred dissolution method
For example, add a dye to a mixed solvent of water and methanol, and
The method of adding equimolar triethylamine to the dye.
I can make it. In the silver halide emulsion used in the present invention
As silver halide grains, silver chloride, silver bromide, chlorobromide
Any of silver, silver iodobromide, silver iodochloride, silver chloroiodobromide, etc.
Can also be used, for example for color photographic paper
Silver chlorobromide milk for the purpose of speeding up and simplifying
The silver chlorobromide emulsion is preferably 95 mol% or more.
Silver chloride, silver chlorobromide, or silver chloroiodobromide
It can be preferably used. Accelerate development processing time
In order to achieve this, silver chlorobromide or silver bromide containing substantially no silver iodide
Is preferably silver chloride. Also color photography
For shadow film (negative and reversal) applications
A silver bromobromide emulsion is preferable, and a silver iodobromide emulsion is 95.
Silver bromide, silver iodobromide, wherein mol% or more is silver bromide, or
Silver chloroiodobromide can be preferably used. Included in the silver halide emulsion used in the present invention.
The average grain size of the silver halide grains (the projected area of the grains)
The particle size is the diameter of the circle equivalent to, and the number average is
(Taken) is preferably 0.1 to 2 μm. Also those
The particle size distribution is a coefficient of variation (standard deviation of particle size distribution).
(Difference divided by average particle size) 20% or less, preferred
Or 15% or less, more preferably 10% or less
Monodispersed ones are preferred. At this time wide latitude
The above monodispersed emulsion is blended in the same layer for the purpose of
It is also preferable to use and layer coating
The Form of silver halide grains contained in photographic emulsion
The shape is like a cube, octahedron, or tetrahedron
With irregular crystal shape, spherical shape, plate shape, etc.
Having a typical crystal form, or a mixture of these
It may consist of In the present invention, these
Above all, particles having the above-mentioned regular crystal form are 50% or more,
Preferably 70% or more, more preferably 90% or more
It is good to do. The emulsions used in the present invention are "C" by P. Glafkides.
himie et Phisique Photographique "(Paul Montel)
(1967), "Photographic Emuls" by G.F.Duffin
ion Chemistry "(Focal Press, 1966), V.
"Making and coating Photographic" by L.Zelikman et al
 Emulsion "(published by Focal Press, 1964)
It can be prepared using the methods described. Snow
I.e. acid method, neutral method, ammonia method, etc.
It is also possible to react a soluble silver salt with a soluble halogen salt.
The following methods are available: one-side mixing method, simultaneous mixing method, and
Any method such as a combination thereof may be used. grain
Method for forming a child under an atmosphere rich in silver ions
(So-called back mixing method) can also be used. Simultaneous mixing
As one form of the method, in the liquid phase where silver halide is formed
A method of keeping pAg constant, that is, a so-called controller
The Ludo double jet method can also be used. This person
According to the method, the crystal form is regular and the particle size is almost uniform
A silver halide emulsion can be obtained. In the emulsion used in the present invention,
More than 50% of the total projected area of silver halide grains, more preferred
70% or more, particularly preferably 80% or more.
Preferably a tabular grain having a mass ratio of 2 or more,
Preferably the aspect ratio is 4 to 1000, more preferred
6 to 500, particularly preferably 8 to 300.
Most preferably, it is 15-200. For example, color
For photographic paper use, silver chlorobromide tabular grains, color photography
For film use, silver iodobromide tabular grains are preferred
Used. In general, tabular grains have two parallel faces.
Therefore, "thickness" constitutes tabular grains
Expressed as the distance between two parallel planes. Halogenated
The diameter of a silver particle is the projection of the particle in an electron micrograph.
The diameter of a circle with an area equal to the area.
The ratio is called the aspect ratio. Of silver chlorobromide used in color photographic paper applications
When the tabular grains are described in detail, the silver chloride content is
80 mol% or more is preferable, and 95% or more of high silver chloride grains
It is more preferable that Silver chlorobromide grains are in the core
And shell containing more iodide than the core
Outer layer). 90% or more core
Is preferably silver chloride. Core part is halogen composition
It may consist of two or more different parts. shell
Part is preferably 50% or less of the total particle volume.
It is particularly preferably 0% or less. Iodization of shell
The silver content is preferably 0.5 to 13 mol%,
It is especially preferable that it is 1-6 mol%. All of silver iodide
The content in the particles is preferably 0.1 to 5 mol%,
˜2 mol% or less is particularly preferred. Contains silver iodide in the core
The amount is preferably 1 mol% or less, in particular 0%
It is preferable. Silver bromide content in the core and shell
May be different. Silver bromide content is 0 with respect to total silver
~ 20 mol% is preferred, 0.1-5 mol% is particularly preferred
That's right. The diameter of the high silver chloride tabular grains is preferably 0.2 to
1.0 μm. Also, the thickness is preferably 0.2μm or less.
Or 0.15 μm or less, particularly preferably 0.1 μm or less.
It is below. The aspect ratio is preferably 3 to 20,
More preferably, it is 5-15. High silver chloride tabular grains
The particle size distribution may be polydisperse or monodisperse,
More preferably, it is dispersed. Dispersion coefficient of particle size
Is preferably 5 to 25%, particularly preferably 5 to 20%.
The dispersion coefficient of the child thickness is also 5 to 25%, particularly 5 to 15%.
It is preferable. High silver chloride used for color photographic paper
In the plate-like particles, the {111} plane is formed as the outer surface
For this purpose, a crystal phase controlling agent is used. Tabular grains are formed in two ways
Is achieved by generating parallel twin planes of
Surface formation is temperature, dispersion medium (gelatin), halogen concentration, etc.
These appropriate conditions must be set.
I have to. When a phase control agent is present during nucleation
The gelatin concentration is preferably 0.1 to 10%. chloride
Concentration is 0.01 mol / liter or more, preferably 0.0
3 mol / liter or more. Crystal phase used specifically
Control agent and {111} high silver chloride flat plate using the same
JP-A-2000-2915 discloses a method for forming the particles.
Those described in No. 6 can be used. Tabular grains have a {100} plane as the main plane.
Tabular grains may be used. The shape of the main plane is a right-angled parallelogram
Missing shape or one corner of the right parallelogram
3 to 5 square shapes (the missing shape is the apex at the corner
And a right triangle formed by the sides forming the corner
Min), or there are 2 or more and 4 or less missing parts 4
There are ~ octagonal shape. Plate with {100} main plane
A method for forming a silver halide emulsion grain is disclosed in, for example,
No. 301129, No. 6-347929, No. 9-340
45, 9-96881, 8-122954,
No. 9-189977. [0146] For use in color photography film applications
In the tabular grains of silver ubromide, the halogen composition is
Contains 30 mol% or less of silver iodide, silver iodobromide, iodine
Silver chloride or silver iodochlorobromide is preferred. Especially preferred
The silver iodobromide containing 2-10 mol% silver iodide
Or silver iodochlorobromide. May contain silver chloride, but preferably
The silver chloride content is preferably 8 mol% or less, more preferably 3
It is less than mol% or 0 mol%. Silver iodobromide flat plate
The diameter of the particles is preferably 0.3 to 5.0 μm
Yes. The thickness of the tabular grains is 0.05 to 0.5 μm
Are preferred. The aspect ratio of the tabular grains is preferably
4-50, more preferably 5-30, still more preferably
6-25. The silver halide emulsion used in the present invention is usually
Chemically sensitized. Chemical sensitization includes so-called gold compounds
Gold sensitization methods (eg, US Pat. No. 2,448,060)
No. 3,320,069), iridium, platinum,
Sensitization with metals such as palladium and palladium (eg, US
Patent Nos. 2,448,060 and 2,566,245
No. 2,566,263), using sulfur-containing compounds
Sulfur sensitizing methods (eg, US Pat. No. 2,222,264)
No.), selenium sensitization using selenium compounds, tellurium compounds
Tellurium sensitization with tin, tin salts, thiodiuresis
Reduction sensitization with silicon, polyamine, etc.
No. 2,487,850, No. 2,518,698, No.
2,521,925). These sensitization methods are independent
Or it can use together. The emulsion used in the present invention is a selenium sensitizer and is chemically
It is preferably sensitized. As a selenium sensitizer
Uses selenium compounds disclosed in conventionally known patents.
Can be. That is, usually unstable selenium compound
Product and / or non-labile selenium compound,
The emulsion is stirred for a certain time at high temperature, preferably 40 ° C. or higher.
Is used. As an unstable selenium compound
Are, for example, Japanese Patent Publication No. 44-15748 and Japanese Patent Publication No. 43-1.
3489, JP-A-4-25832, JP-A-4-10
It is preferable to use the compound described in No. 9240. Ingredients
As a physical labile selenium sensitizer,
Fats such as allyl isoselenocyanate
Aliphatic isoselenocyanates), selenoureas, seleno
Ketones, selenoamides, selenocarboxylic acids (eg
2-selenopropionic acid, 2-selenobutyric acid), selenium
Ester, diacyl selenide (for example, bis (3
-Chloro-2,6-dimethoxybenzoyl) seleni
D), selenophosphates, phosphine selenides,
Examples include colloidal metal selenium. Preferred types of unstable selenium compounds are listed above.
However, these are not limiting. Engineer
Instability selenium compounds as sensitizers for photographic emulsions
For example, as long as selenium is unstable,
The structure is not important, and the selenium sensitizer molecule
The organic part carries selenium, which is unstable in the emulsion.
In general, it has no role other than its presence
Understood. In the present invention, such a broad concept
These labile selenium compounds are advantageously used. Non-labile selenium compound used in the present invention
As a thing, Japanese Examined Sho 46-4553, Japanese Examined Sho 52-34
Compounds described in No. 492 and JP-B 52-34491
Things are used. An example of a non-labile selenium compound
Selenite, potassium selenocyanide, selenazole
, Quaternary salts of selenazoles, diaryl selenides, di
Aryl diselenide, dialkyl selenide, dialkyl
Diselenide, 2-selenazolidinedione, 2-selenoo
Xazolidinethione and their derivatives
The Of these selenium compounds, preferably
Japanese Patent Application Laid-Open No. 11-15115, general formula (VII)
And those of (VIII) are preferably used. These secs
Len sensitizers are water or methanol, ethanol, etc.
Dissolved in a single solvent or a mixed solvent and added during chemical sensitization
Is done. Preferably, it is added before the start of chemical sensitization. use
The selenium sensitizer to be used is not limited to one.
Two or more agents can be used in combination. Unstable
The combined use of a ren compound and a non-labile selenium compound is preferred.
The amount of selenium sensitizer added depends on the activity of the selenium sensitizer used.
Degree, type and size of silver halide, temperature and time of ripening
Preferably, the emulsion is halogenated.
1 x 10 per mole of silver^-8More than moles. More preferable
Is 1 × 10^-7~ 5x10^-FiveIs a mole. Selenium sensitizer
When used, the temperature of chemical ripening is preferably 45 ° C or higher.
is there. More preferably, it is 50-80 degreeC. pAg and
PH is arbitrary. For example, the pH is wide from 4 to 9.
The effects of the present invention can be obtained within the range. The silver halide emulsion used in the present invention has a sensitivity.
Fog during optical material manufacturing process, storage or photo processing
For the purpose of preventing or stabilizing photographic performance
Various compounds or their precursors can be added
Yes. Specific examples of these compounds are described in JP-A-62-2.
Described in pages 15 to 72 of the specification of No. 15272
Those are preferably used. Further EP 0447647
5-Arylamino-1,2,3,4-thiatria
Sol compound (the aryl residue has at least one electric
(Having a child attractive group) is also preferably used. Silver halide emulsions prepared according to the present invention
Is either a color photographic material or a black-and-white photographic material
Can also be used. As a color photographic material
Especially color photographic paper, film for color photography, color river
-Sal film, black and white photographic material for X-ray
Film, film for general photography, film for printing material, etc.
Can be mentioned. For the preparation of photographic emulsions used in the present invention, etc.
About column 63 of JP-A-10-239789
36th line to 65th column, 2nd line, etc. can be applied. Color cards
The present invention is suitable for additives such as pullers and photographic material additives.
Types of photosensitive materials used, processing of photosensitive materials, etc.
Is disclosed in JP-A-10-239789, column 65, line 3
˜73rd column, 13th row can be applied. The silver halide photographic light-sensitive material of the present invention includes
The above-mentioned various additives are used, but other purposes
Various additives can be used depending on the case. these
Additives are more detailed in Item 1 of Research Disclosure
7643 (December 1978), Item 18716 (1979)
November) and Item 308119 (December 1989)
The corresponding locations are summarized in the table below.
did. [0156]   Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 page 648 right column page 996 2 Sensitivity increasing agent Same as above 3 Spectral sensitizers, 23-24 pages 648, right column-996 right-998 right     Supersensitizer 649 pages, right column 4 Brightener 24 pages 998 right 5 Antifoggant 24-25 pages 649 right column 998 right-1000 right     And stabilizer 6 Light Absorber, Fill 25-26 pages 649, right column-1003 left-1003 right     Left column on page 650 7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, Lubricant 27 pages 650 pages right column 1006 left to 1006 right 12 Application aid, pages 26-27 Same as above 1005 left-1006 left     Surfactant 13 Antistatic agent Page 27 Same as above 1006 Right to 1007 Left 14 Matting agent 1008 left to 1009 left Emulsion used in the present invention and its emulsion
Techniques such as layer arrangement that can be used for photographic materials
, Silver halide emulsion, dye-forming coupler, DIR cup
And other functional couplers, various additives, and development
Regarding the processing, European Patent No. 0565096A1 (1
(Released October 13, 993) and the features cited in this
It is written in the permit. Below is a description of each item and the corresponding item.
List the locations. [0158] 1. Layer structure: 61 pages 23-35 lines, 41 lines 62 pages 14 lines 2. Middle layer: 61 pages 36-40 lines 3. Multi-layer effect layer: 62 pages 15-18 lines 4). Silver halide halogen composition: 62 pages 21-25 5). Silver halide grain habit: 62 pages 26-30 6). Silver halide grain size: 62 pages 31-34 7). Emulsion production method: 62 pages 35 to 40 lines 8). Silver halide grain size distribution: 62 pages 41-42 9. Tabular grains: 62 pages 43-46 Ten. Particle internal structure: 62 pages 47-53 lines 11． Emulsion latent image formation type: 62 pages, 54 lines to 63 pages, 5 lines 12． Emulsion physical ripening / chemical sensitization: p. 63, lines 6-9 13. Emulsion mixed use: 63 pages 10-13 14. Kabaze emulsion: p. 63, lines 14-31 15． Non-light-sensitive emulsion: 63 pages, lines 32 to 43 16． Amount of applied silver: 63 pages, 49-50 lines [0159] 17． Formaldehyde scavenger: 64 pages 54-57 lines 18． Mercapto-type antifoggant: 65 pages 1-2 lines 19. Release agent such as fogging agent: 65 pages 3-7 lines 20． Dye: 65 pages 7-10 lines twenty one. Color couplers in general: 65 pages, lines 11-13 twenty two. Yellow, magenta and cyan couplers: 65 pages 14-25 twenty three. Polymer coupler: 65 pages 26-28 lines twenty four. Diffusible dye-forming coupler: 65 pages 29-31 twenty five. Colored coupler: 65 pages 32 to 38 lines 26. Functional couplers in general: 65 pages 39-44 27. Bleach accelerator releasing coupler: 65 pages 45-48 28. Development accelerator releasing coupler: p. 65, lines 49-53 29. Other DIR couplers: page 65, line 54 to page 66, line 4 30. Coupler dispersion method: 66 pages 5 to 28 lines [0160] 31. Preservatives and fungicides: Page 66, lines 29-33 32. Type of sensitive material: 66 pages 34-36 33. Photosensitive layer thickness and swelling speed: 66 pages 40 lines to 67 pages 1 line 34. Back layer: 67 pages 3-8 lines 35. General development processing: 67 pages, lines 9-11 36. Developer and developer: p. 67, lines 12-30 37. Developer additive: Page 67, lines 31-44 38. Inversion processing: 67 pages 45-56 lines 39. Treatment liquid opening ratio: 67 pages 57 lines to 68 pages 12 lines 40. Development time: 68 pages 13-15 lines 41. Bleaching / Bleaching / Fixing: 68 pages, 16 lines to 69 pages, 31 lines 42. Automatic processor: 69 pages, 32-40 lines 43. Flushing, rinsing and stabilization: 69 pages 41 lines to 70 pages 18 lines 44. Treatment liquid replenishment / reuse: p. 70, lines 19-23 45. Built-in developer sensitive material: 70 pages 24 to 33 lines 46. Development processing temperature: 70 pages 34-38 lines 47. Use with lens film: 70 pages 39-41 [0161] EXAMPLES The present invention will be specifically described below with reference to examples.
However, the present invention is not limited to this. Example 1 (Preparation of {111} high silver chloride tabular grains)
2.0 g NaCl and inactive gelatin 2.4 in the torr
AgN with stirring into a container added with g and kept at 33 ° C
O_Three 60cc of aqueous solution (AgNO_Three9g) and aqueous NaCl
Liquid 60cc (NaCl3.2g) to double jet method
More in 1 minute. 1 minute after completion of addition
1 mmol of 1 was added. After another minute, NaCl3.
0 g was added. Over the next 25 minutes, the temperature of the reaction vessel is increased to 60
The temperature was raised to ° C. After aging at 60 ° C for 16 minutes,
290 g of an aqueous solution of gelatinized tartar and crystal phase controlling agent-1
8 mmol was added. After this, AgNO_Three Aqueous solution 754
cc (AgNO_Three 113 g) and an aqueous NaCl solution 768c
c (NaCl 41.3 g) was accelerated over 28 minutes
Added at flow rate. During this time, it takes 21 to 28 minutes.
I (addition amount is 0.5% of the outermost layer iodine content)
Amount), 11 mg yellow blood salt and iridium hexachloride
1.5 × 10^-80.25M NaCl aqueous solution containing 1 mol
30 cc was added. After addition, 1% potassium thiocyanate
5.6 cc of um and the sensitizing dyes listed in Table 1
It was. Thereafter, the temperature was raised to 75 ° C. and stirring was continued for 10 minutes.
After lowering the temperature to 40 ° C.
The desalting process was performed by the flocculation method. Desalting
After that, add 67g of gelatin and 80cc of phenol (5%)
And 150 cc of distilled water was added. Sodium hydroxide
And AgNO_ThreeAdjust to pH 6.2, pAg 7.5 with solution
It was. Thus, 96% of the total projected area has an average sphere equivalent diameter of 0.
65μm, average equivalent circle diameter of 1.19μm, average thickness
A tabular grain with an average aspect ratio of 9.1
Emulsions 101 to 129 containing children were obtained. (Chemical sensitization) Emulsions 101 to 129 at 60 ° C
Sodium thiosulfonate, 1- (5-methylureido
Phenyl) -5-mercaptotetrazole, selenium compound
Product-1, sodium thiosulfate and chloroauric acid
Chemical sensitization was performed appropriately. [0163] Embedded image [0164] Embedded image [0165] Embedded image (Preparation of coated sample) Polyethylene on both sides of the paper
Corona discharge treatment on the surface of the support coated with resin
After applying sodium dodecylbenzenesulfonate
A gelatin subbing layer containing the first layer to the seventh layer
The photographic composition is applied in sequence, and the halogen of the layer structure shown below
Samples 101 to 109 of silver halide color photographic light-sensitive material were prepared.
It was. The coating solution for each photographic composition layer is prepared as follows.
It was. Preparation of coating solution Coupler, color image stabilizer, UV absorber solvent and acetic acid
Dissolve in ethyl and add 10% by mass of this solution with surfactant.
High-speed stirring emulsifier (dissolver) in gelatin aqueous solution
Emulsified and dispersed, and water was added to prepare an emulsified dispersion. The milk
The mixed dispersion and high silver chloride emulsion are mixed and dissolved to obtain the composition described below.
A coating solution was prepared as described above. As a gelatin hardener for each layer, 1-oxy
-Uses 3,5-dichloro-s-triazine sodium salt
It was. In addition, each layer has Ab-1, Ab-2 and Ab-3.
The total amount is 15.0 mg / m²60.0 mg /
m²And 5.0 mg / m² It added so that it might become. [0169] Embedded image The high silver chloride emulsion used in each photosensitive emulsion layer is as follows.
It is as follows. (Blue-sensitive emulsion layer) The aforementioned silver chloride tabular emulsion was used. (Green photosensitive emulsion layer) Silver chlorobromide emulsion (cube, average grain size)
Large size emulsion of 0.45μm and small size of 0.35μm
1: 3 mixture with silver emulsion (silver molar ratio). Particle size
The coefficient of variation is 10% and 8%. Bromide for each size emulsion
0.4 mol% of silver is part of the grain surface based on silver chloride
Sensitizing dye G1 is added to the silver halide
3.0 x 1 for each large emulsion
0^-Four3.6 × 1 each for molar and small emulsions
0^-FourMole was added. In addition, the sensitizing dye G2 is halogenated.
4. For each large silver emulsion per mole of silver
0x10^-FiveFor molar and small emulsions, 2.
8 × 10^-FourMole was added. [0171] Embedded image(Red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic)
A large emulsion A having an average grain size of 0.50 μm,
1: 4 mixture with 0.41 μm small size emulsion B (silver module)
Le ratio). The coefficient of variation of particle size is 0.09 and 0.11.
For each size emulsion, 0.8 mol% silver bromide based on silver chloride
And localized in a part of the particle surface). Sensitizing dye R
1 and R2 large size per mole of silver halide
6.0 × 10 for each emulsion^-FiveMole, small size
9.0 × 10 for each emulsion^-FiveMole was added. [0173] Embedded image Further, the following compound-I was converted to silver halide.
2.6 x 10 per mole^-3Mole was added. [0175] Embedded image Also, blue-sensitive, green-sensitive and red-sensitive emulsion layers
In contrast, 1- (3-methylureidophenyl) -5-methyl
Lucatotetrazole, 1 mol of silver halide each
3.3 × 10 per^-FourMol, 1.0 × 10^-3Mole and
5.9 × 10^-FourMole was added. Second layer, fourth
Layer, sixth layer and seventh layer are each 0.2 mg / m
²0.2 mg / m²0.6 mg / m²And 0.1m
g / m²It added so that it might become. In the red sensitive emulsion layer
Copolymer of methacrylic acid and butyl acrylate (mass ratio
1: 1, average molecular weight 200000-400000)
0.05g / m²Added. Second layer, fourth layer and
And the sixth layer catechol-3,5-disulfonic acid dinatri
Each 6mg / m²6 mg / m²And 18m
g / m²It added so that it might become. In addition, irradiation
The following dyes are applied to the emulsion layer (in parentheses are coated)
Represents the amount). [0177] Embedded image (Layer structure) The layer structure is shown below. The numbers are painted
Cloth amount (g / m²). Silver halide emulsion is silver equivalent
Represents the amount of cloth. Support: Polyethylene resin laminated paper [White pigment (TiO 2 on the first layer side polyethylene resin)₂Contained
16% by mass, ZnO; content 4% by mass) and optical brightener
(4,4'-bis (5-methylbenzoxazolyl) s
Tilben 13mg / m²), 96 bluish dye (ultraviolet)
mg / m²Including] [0179] First layer (blue sensitive emulsion layer)   Emulsion 0.24   Gelatin 1.25   Yellow coupler (ExY) 0.57   Color image stabilizer (Cpd-1) 0.07   Color image stabilizer (Cpd-2) 0.04   Color image stabilizer (Cpd-3) 0.07   Color image stabilizer (Cpd-4) 0.02   Solvent (Solv-1) 0.21 [0180] Second layer (color mixing prevention layer)   Gelatin 0.60   Color mixing inhibitor (Mid-1) 0.10   Color mixing inhibitor (Mid-2) 0.18   Color mixing inhibitor (Mid-3) 0.02   Ultraviolet absorber (UV-C) 0.05   Solvent (Solv-5) 0.11 [0181] Third layer (green sensitive emulsion layer)   Emulsion 0.14   Gelatin 0.73   Magenta coupler (ExM) 0.15   Ultraviolet absorber (UV-A) 0.05   Color image stabilizer (Cpd-2) 0.02   Color mixing inhibitor (Cpd-3) 0.008   Color image stabilizer (Cpd-4) 0.08   Color image stabilizer (Cpd-5) 0.02   Color image stabilizer (Cpd-6) 0.009   Color image stabilizer (Cpd-7) 0.0001   Solvent (Solv-3) 0.06   Solvent (Solv-4) 0.11   Solvent (Solv-5) 0.06 [0182] Fourth layer (color mixing prevention layer)   Gelatin 0.48   Color mixing inhibitor (Mid-4) 0.07   Color mixing inhibitor (Mid-2) 0.006   Color mixing inhibitor (Mid-3) 0.006   UV absorber (UV-C) 0.04   Solvent (Solv-5) 0.09 [0183] 5th layer (red-sensitive emulsion layer)   Emulsion 0.12   Gelatin 0.59   Cyan coupler (ExC-A) 0.13   Cyan coupler (ExC-B) 0.03   Color mixing inhibitor (Mid-3) 0.01   Color image stabilizer (Cpd-5) 0.04   Color image stabilizer (Cpd-8) 0.19   Color image stabilizer (Cpd-9) 0.04   Solvent (Solv-5) 0.09 [0184] Sixth layer (UV absorbing layer)   Gelatin 0.32   Ultraviolet absorber (UV-C) 0.42   Solvent (Solv-7) 0.08 [0185] Seventh layer (protective layer)   Gelatin 0.70   Acrylic modified polymer of polyvinyl alcohol (degree of modification 17%) 0.04   Liquid paraffin 0.01   Surfactant (Cpd-13) 0.01   Polydimethylsiloxane 0.01   Silicon dioxide 0.003 [0186] Embedded image [0187] Embedded image[0188] Embedded image[0189] Embedded image[0190] Embedded image [0191] Embedded image[0192] Embedded image [0193] Embedded imageIn the manner as described above, the coated samples 101 to 1
09 was created. (Exposure) B, G, R, 3 colors
The tone of the three color separation was exposed with the zir light. At that time, each trial
Laser power to ensure optimal improvement over the charge
Was corrected. Also, the sample was 50 ° C. and 70% R.D. H. 1
After storage for 50 hours, the sensitivity is evaluated by exposure and processing in the same way.
did. (These are the sensitivity after storage.) (Exposure apparatus) The light source is a semiconductor laser GaAl.
YAG solid-state laser using As (oscillation wavelength 808.5nm) as excitation light source
-LiNbO with inverted domain structure (oscillation wavelength 946nm)
_Three473nm extracted by wavelength conversion with SHG crystal of
Conductor laser GaAlAs (oscillation wavelength 808.5nm) as excitation light source
YVO4 solid state laser (oscillation wavelength 1064nm) inverted domain
LiNbO with a structure_ThreeWavelength conversion using SHG crystal
532nm and AlGaInP (oscillation wavelength 680nm: Matsushita Electric)
Manufactured type No. LN9R20). Each of the three colors
The light is intensity-modulated by the AOM and runs by a polygon mirror.
Move in the direction perpendicular to the inspection direction, on the color photographic paper,
Sequential scanning exposure was made possible. Semiconductor laser temperature
The light intensity fluctuation due to the temperature is constant using the Peltier element
It is suppressed by being kept in. This scanning exposure is 60
0dpi, a light beam diameter measuring device [1180GP / beam scan
In the measurement of the light beam diameter using
G and R were both 65 μm (main scanning direction diameter / sub-scanning direction)
It was a circular beam with a difference in diameter within 1%). (Development processing; dry to dry 55 seconds)
Color development processing on samples using the following processing steps and processing solutions
Was given. Processing temperature Temperature Time Replenisher^*tank capacity Color development 45 ℃ 15 seconds 35ml 2L Bleach fixing 40 ° C 15 seconds 38ml 1L Rinse 40 ℃ 5 seconds ――― 1L Rinse 40 ℃ 5 seconds ――― 1L Rinse 40 ° C 5 seconds 90ml 1L Drying 80 ℃ 10 seconds ――― ――― (The tank counter-flow system was used for rinsing →) * Photosensitive material 1m²Replenishment amount per In the above treatment, the water for rinsing is a reverse osmosis membrane.
The permeated water is supplied to the rinse and passed through the reverse osmosis membrane.
The concentrated water that was not used was returned to the rinse and used. In addition,
Between rinses to reduce crossover time
A blade was installed on the surface, and the photosensitive material was passed therethrough. Ma
In each step, spraying described in JP-A-8-314088
The spraying amount is 4-6L / min per tank using the equipment.
It set and sprayed the circulation processing liquid. The composition of each processing solution is as follows. Color developer Tank solution Replenisher 700ml water 700ml Sodium triisopropylnaphthalene (β) sulfonate                                               0.1g 0.1g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt                                               0.5g 0.5g Triethanolamine 12.0g 12.0g Potassium chloride 15.8g ――― Potassium bromide 0.04g ――― Potassium carbonate 27.0g 27.0g Sodium sulfite 0.1g 0.1g Disodium N, N-bis (sulfonatoethyl) hydroxylamine                                             18.0g 18.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Noaniline sulfate                                               8.0g 23.0g Sodium bis (2,4-disulfonatoethyl-1,3,5-triazine-6 -Yl) diaminostilbene-2,2-disulfonate                                             5.0g 6.0g Add water 1000ml 1000ml pH (25 ° C.) 10.35 12.80 The bleach-fixing solution is a two-component replenisher as follows:
And mixed. Bleach-fixing solution Tank solution Replenishment amount (1m in the following amount)²(Total 38ml) 1st replenisher 260ml 18ml Second replenisher 290ml 20ml 1000ml with water pH (25 ° C) 5.0 The composition of the first and second replenishers is as follows:
It is. (First replenisher) 150ml water Ethylene bisguanidine nitrate 30g Ammonium sulfite monohydrate 226g Ethylenediaminetetraacetic acid 7.5g 1.0g triazinylaminostilbene fluorescent whitening agent (Showa Chemical Hakkol FWA-SF) 30 g of ammonium bromide Ammonium thiosulfate (700 g / L) 340 ml 1000ml with water pH (25 ° C.) 5.82 (Second replenisher) 140 ml of water Ethylenediaminetetraacetic acid 11.0g Ethylenediaminetetraacetic acid iron (III) ammonium 384 g Acetic acid (50%) 230ml 1000ml with water pH (25 ° C.) 3.35 (Rinse solution) Ion exchange water (Ca, Mg 3ppm or less each) (Comparison process) Reduced water washing time for comparison
CP45-X treatment (dry to d
ry 130 seconds). Each process of color development and bleach-fixing = 45 seconds, rinse, re-
Each step of the process = 20 seconds. [0220] The developed color sample was treated with Fuji Photo Film.
The reflection density was measured using a TCD type density measuring device manufactured by
It was. Sensitivity gives color density 1.0 higher than fog density
It was determined from the amount of exposure necessary to Blue sensitivity is 130 seconds
Expressed as a relative value with the sensitivity of the sample 101 taken as 100
It was. Fog is a coupler by developing unexposed areas.
And the residual color of the sensitizing dye. Table 1 shows the measurement results.
The [0203] [Table 1] [0204] Embedded image As can be seen from the results in Table 1, one embodiment of the present invention.
Compound represented by general formula (Ia), (Ib), or (Ic)
And (II-3) of the compound represented by the general formula (II), S-1
Sufficient sensitivity cannot be obtained when each is used alone.
As well as fogging (caused by residual color of sensitizing dye)
The tendency was remarkable in rapid processing.
Furthermore, the sensitivity drop after storage was also remarkable. This problem
It was not solved by the combined use of (II-3) and S-1. This
Compared to these, when the dye is used in combination in the embodiment of the present invention,
Significantly improved sensitivity and reduced residual color after photo processing
In addition, the sensitivity reduction after storage can be significantly suppressed.
I found out. As described above, the dye in the embodiment of the present invention
Only when used together, unique without deteriorating the residual color
In particular, an emulsion that has a high sensitivity and further suppresses a decrease in sensitivity after storage.
It was found that it can be obtained. Example 2 (Preparation of sample 201) JP-A-11-119365
In accordance with the method for preparing the sample 101 in Example 1 described in the
A layer color photosensitive material was prepared and used as Sample 201. Sample 2
The photosensitive emulsion used in 01 is shown in Table 2. [0207] [Table 2] Note 1) All of the above emulsions are gold, sulfur and selenium.
This is a silver iodobromide emulsion chemically sensitized with benzene. Note 2) In all the above emulsions, sensitizing dye is added before chemical sensitization.
doing. Note 3) For the above emulsion, JP-A-11-119365
Compounds F-5, F-7, F-8, F-9, F-1
0, F-11, F-12, F-13, F-14
It is added. Note 4) Emulsions A, B, I and J have a main plane of (100) and others
Is a triple-structure tabular grain having a main plane of (111). Note 5) Emulsions A, B, E, F, I and P are more internal than surface sensitivity.
It is an emulsion with higher sensitivity. Note 6) Emulsions E, I, and P are epitaxially treated with silver chloride after chemical sensitization.
This is a particle that has been grown. Note 7) 50 grains per grain for grains other than emulsions A, E, and F
These dislocations are particles observed with a transmission electron microscope.
The (Preparation and evaluation of samples 200, 202 to 204)
Value) Sensitized colors of emulsions C to E used in sample 201
By replacing element S-2 with equimolar as shown in Table 3,
202-204, and dye blank test by removing the dye
Material 200 was prepared. The sample piece obtained in this way is 1 /
With a 100 second exposure time and 20 CMS exposure,
After the white exposure through the wedge,
And sensitometry was performed. Sample 6
0 ° C., 80% R.D. H. After 120 hours storage
The sensitivity was evaluated by light and treatment. (Sensitivity after storage
And ) Also, the magenta-cyan density of the stained specimen
To magenta-cyan stay of dye blank sample 200
The residual color was evaluated by subtracting the density of the toner. Stain concentration is
Measure with the X-RITE concentration meter, Status A
It was. Furthermore, a pattern for RMS value measurement is passed to each sample.
And a halogen lamp with a color temperature of 3200 ° K as the light source
The samples exposed using
RMS value measured with a radiometer (measurement aperture diameter 48μm)
Asked. [0210] (processing)   Processing time Time Temperature Tank capacity Replenishment amount   First development 6 minutes 38 ℃ 12L 2200 ml / m²   First water wash 2 minutes 38 ℃ 4L 7500 ml / m²   Inversion 2 minutes 38 ℃ 4L 1100 ml / m²   Color development 6 minutes 38 ℃ 12L 2200 ml / m²   Pre-bleaching 2 minutes 38 ℃ 4L 1100 ml / m²   Bleaching 6 min 38 ℃ 2L 220 ml / m²   Fixing 4 minutes 38 ℃ 8L 1100 ml / m²   Second water wash 2 minutes 38 ℃ 8L 7500 ml / m²   Final rinse 1 min 25 ℃ 2L 1100 ml / m² The composition of each treatment solution is disclosed in JP-A-11-11936.
It is the same as that of Example 1 described in No. 5 specification. Table 3 below shows sensitometry, residual color and
The evaluation results of graininess and sensitivity after storage are shown. Red relative sensitivity
Is a comparison based on the relative exposure from 1.0 to 1.0
(The sensitivity of the sample 201 is 100). RMS value is
For the value of cyan image density 0.7, the value of sample 201
Is shown as a relative value when the value is 100 (the smaller the value,
Good graininess). [0213] [Table 3] [0214] Embedded imageAs is apparent from the results in Table 3, the present invention
Formulas represented by general formula (Ia), (Ib), or (Ic)
Compound, and a compound represented by the general formula (II) ((II-23), S
-2 and (II-26) were used in combination with a dye in the embodiment of the present invention.
In this case, a significant improvement in sensitivity and an improvement in graininess were confirmed.
Also, there was almost no deterioration of the residual color. Further feeling after storage
Degradation was suppressed. As described above, in the embodiment of the present invention
Only when the dye is used in combination, the residual color is deteriorated.
Achieves both sensitivity and graininess without any loss, and sensitivity after storage
It was found that an emulsion in which the decrease in the thickness was suppressed was obtained. Example 3 (Preparation of sample 301) JP-A-11-305396
In accordance with the method for preparing the sample 101 in Example 1 described in the
A layer color photosensitive material was prepared and used as Sample 301. The AgI content of the emulsion used and the grain size
Table 4 below shows the surface iodine content and the like. [0218] [Table 4] In Table 4, (1) Emulsions L to O are examples of JP-A-2-191938
In accordance with thiourea dioxide and thiosulfonic acid
Reduction sensitization is performed at the time of preparation of the baby. (2) Emulsions A to O are examples of JP-A-3-237450
In accordance with the spectral sensitizing dye and thiocyanic acid described in each photosensitive layer
Gold, sulfur and selenium sensitization in the presence of sodium
It has been subjected. (3) JP-A-1-158426 is used for preparing tabular grains.
In accordance with the examples, low molecular weight gelatin is used. (4) Tabular grains described in JP-A-3-237450
Observed dislocation lines using a high-voltage electron microscope
Has been. (Production of Samples 302 and 303) Sample 30
The sensitizing dyes of the 10th and 11th layers of No. 1 are sensitized in Table 5 below.
Samples 302 and 303 were the same except that the dye was changed.
It was created. The sensitivity and fog of the above samples are as follows.
The method was evaluated. Also, the sample was 60 ° C. and 80% R.D.
H. , 120 hours after storage, exposure and processing in the same way
The degree was evaluated. (These are the sensitivity after storage.) Continuous wedge and Fuji with color temperature of 4800 ° K
Photo Film Co., Ltd. Gelatin Filter SC-50
Sensitometric exposure through 1/100 second through
The following color development processing was performed. (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Whitening 3m00s 38 ℃ Washing with water 30 seconds 24 ° C Settling time 3 minutes 00 seconds 38 ° C Washing with water (1) 30 seconds 24 ° C Washing with water (2) 30 seconds 24 ° C Stable 30 seconds 38 ° C Dry 4 minutes 20 seconds 55 ° C The composition of each processing solution is disclosed in JP-A-11-30539.
It is the same as that of Example 1 described in No. 6 specification. Samples 301 to 303 subjected to the above development processing.
The magenta density was measured. Sensitivity depends on optical density.
The reciprocal of the exposure required to be 0.2 higher than yellowtail
The relative value of the sample 301 is shown as 100.
Fog is the color of the unexposed coupler and the remaining sensitizing dye.
Consists of colors. The results are shown in Table 5 below. [0225] [Table 5] [0226] Embedded image As is apparent from the results in Table 5, the general formula
(II) ((II-20), (S-5), (II-13)) combined
Compared to the sample, the general formulas (Ia), (Ib),
Is represented by the compound represented by (Ic) and the general formula (II)
When used in combination with compounds, there is less residual color
A high-quality silver halide photographic material can be obtained.
Karu. In addition, a decrease in sensitivity after storage is significantly suppressed.
I understood. As described above, the dye is used together in the embodiment of the present invention.
In particular, the sensitivity is high and the residual color is low.
Found that emulsions with little loss of sensitivity
It was. Example 4 Silver bromide octahedral emulsion (emulsion A) and silver bromide tabular emulsion (milk)
Preparation of Agent B, Emulsion C, Emulsion D, and Emulsion E). Reaction vessel
1000ml water, deionized bone gelatin 25
g, 50% NH_FourNO_Three15 ml of aqueous solution and 25%
NH_ThreeAdd 7.5ml of aqueous solution and keep at 50 ° C.
750 ml of 1N silver nitrate aqueous solution and 1 mol / l
Of potassium bromide solution in 50 minutes.
The position was kept at -40 mV. The obtained silver bromide grains are octahedral.
The equivalent sphere diameter was 0.846 ± 0.036 μm.
Reduce the temperature of the emulsion, isobutene and maleate
Add a copolymer with thorium salt as a flocculant,
Washed and desalted. The deionized bone gelatin 9
5 g and 430 ml of water were added, pH 6.5 at 50 ° C,
And adjusted to pAg 8.3 so that the optimum sensitivity is obtained.
Potassium thiocyanate, chloroauric acid and sodium thiosulfate
Um was added and aged at 55 ° C. for 50 minutes. Milk this emulsion
Agent A was designated. Potassium bromide 6.4 in 1.2 liters of water
g and low molecular weight gelatin having an average molecular weight of 15,000 or less
16.4% silver nitrate with 2g dissolved and kept at 30 ° C
8.1 ml of aqueous solution and 23.5% potassium bromide aqueous solution
Add 7.2ml over 10 seconds by double jet method
did. Next, add 11.7% aqueous gelatin solution.
After heating to 75 ° C and aging for 40 minutes, 32.2% glass
370 ml of silver acid aqueous solution and 20% potassium bromide aqueous solution
For 10 minutes while maintaining the silver potential at -20 mV.
The temperature was lowered to 35 ° C. after physical aging for 1 minute. This
Thus, the average projected area diameter is 2.32 μm, and the thickness is 0.0.
9 μm (aspect ratio 25.8), diameter variation coefficient 1
5.1% monodispersed pure silver bromide tabular emulsion (specific gravity 1.15)
Obtained. Thereafter, soluble salts were removed by a coagulation precipitation method.
Again maintain the temperature at 40 ° C., 45.6 g gelatin, 1 mo
10 ml of 1 / l sodium hydroxide aqueous solution, water
167 ml, and 35% phenoxyethanol
66ml was added, and pAg was adjusted to 8.3 and pH to 6.20.
Arranged. This emulsion is thiocyanated for optimum sensitivity.
Potassium acid, chloroauric acid and sodium thiosulfate added
Aged at 55 ° C. for 50 minutes. This emulsion is called Emulsion B
It was. Also, potassium thiocyanate, chloroauric acid and
And potassium thiocyanate instead of sodium thiosulfate
Um, chloroauric acid, pentafluorophenyl-diphenyl
Chemistry with phosphine selenide and sodium thiosulfate
The sensitized emulsion was designated as Emulsion C. In addition, in adjusting emulsion B, the silver potential was adjusted.
By adjusting, average projected area diameter 1.56μm, thickness
0.625μm (aspect ratio 2.5), diameter variation
Monodispersed pure silver bromide tabular emulsion with a coefficient of 15.1% (specific gravity 1.1
6), and further processed and chemically sensitized in the same manner as emulsion D
It was. In addition, in adjusting emulsion B, the silver potential was adjusted.
By adjusting, average projected area diameter 2.12μm, thickness
0.341μm (aspect ratio 6.2), variation in diameter
Monodispersed pure silver bromide tabular emulsion with a coefficient of 15.0% (specific gravity 1.1
6), and further processed and chemically sensitized in the same manner to obtain Emulsion E
It was. Furthermore, in the preparation of emulsion B, the silver potential was
By adjusting, the average projected area diameter 2.36 μm,
0.274μm thickness (aspect ratio 8.6), diameter change
Monodispersed pure silver bromide tabular emulsion with a dynamic coefficient of 15.1% (specific gravity 1.
15), and further processed and chemically sensitized to obtain an emulsion.
F. The emulsion obtained as described above was heated to 50 ° C.
While maintaining, add the dye shown in Table 6 and stir for 60 minutes.
It was. In addition, gelatin emulsion hardener, and
A coating aid is added, and the coating silver amount is 3.0 g-Ag / m.²In
On the cellulose acetate film support
And simultaneously coated with a gelatin protective layer. Obtained
Film sample (fresh sample) with tungsten bulb (color
Continuous wedge color filter for temperature 2854K)
And exposed for 1 second. Encourage the dye side as a color filter
Fuji gelatin filter SC for negative blue exposure
-40 nm (manufactured by FUJIFILM Corporation)
The lower light was blocked and the sample was irradiated. The exposed sample is
Using the above surface developer MAA-1 for 10 minutes at 20 ° C.
I imaged it. Next, fix the following, and then wash and dry it.
I did it. Further, the film sample was placed at 50 ° C. and 70 ° C.
% R. H. , After 150 hours storage (sample after storage)
The same exposure and processing were performed. Surface developer MAA-1 Metol 2.5g 10g of L-ascorbic acid Nabox (FUJIFILM Corporation) 35g Potassium bromide 1g 1 liter with water pH 9.8 Fixer formulation 170g ammonium thiosulfate Sodium sulfite (anhydrous) 15g 7g of boric acid Glacial acetic acid 15ml Potash alum 20g Ethylenediaminetetraacetic acid 0.1g Tartaric acid 3.5g 1 liter with water Film samples subjected to development and other processing
Measures the optical density with Fuji automatic densitometer, and the sensitivity is +
Evaluated by the reciprocal of the amount of light required to give an optical density of 0.2
When the sensitivity of each fresh sample is 100
The sensitivity of the sample after storage was shown as a relative value. [0239] [Table 6]The total amount of dye added is Samples 61-65: 2.1 × 10^-Fourmol / molAg
(Samples 64 and 65 are added with each dye 1: 1), Sample 66-70: 3.3 × 10^-Fourmol / molAg
(Samples 69 and 70 are added at 1: 1 for each dye), Samples 71-75: 4.3 × 10^-Fourmol / molAg
(Samples 74 and 75 are added with each dye 1: 1), Sample 76-80: 5.2 × 10^-Fourmol / molAg
(Samples 79 and 80 are added with each dye 1: 1), Sample 81-92: 9.2 × 10^-Fourmol / molAg
(Samples 84, 85, 90, 91, and 92 are each dye 1: 1.
Addition). [0241] Embedded image From the results shown in Table 6, the dyes were combined in the embodiment of the present invention.
The sample used was less sensitive after storage than the comparative sample.
I understand that there are few. In addition, sensitivity after storage of comparative samples
Is a tabular emulsion D, E, F,
The sensitivity drop is larger at B, and the degree is high aspect ratio
(In particular, the aspect ratio is 8 or more)
Karu. In contrast, a test using a dye in combination with the embodiment of the present invention.
The sensitivity after storage of the slab is higher than that of octahedral emulsion A.
D, E, F, and B of the agent are less sensitive, and the extent
Has a high aspect ratio (especially an aspect ratio of 8 or more)
You can see how big it is. Also compare emulsions B and C
And selenium-sensitized Emulsion C significantly improves storage stability
I understand that [0243] According to the constitution of the present invention, the dissolution aging stability is improved.
High, high sensitivity and excellent graininess
Halogen with little residual color afterwards and low sensitivity loss after storage
A silver halide photographic light-sensitive material can be obtained.

Claims (1)

[Claims] 1. Halogenation of at least one layer on a support
In a silver halide photographic light-sensitive material containing a silver photographic emulsion layer.
In the emulsion layer, the following general formulas (Ia), (Ib), and
And at least one selected from compounds represented by (Ic)
Less species and compounds represented by the following general formula (II)
Silver halide photographic sensation characterized by containing at least one
Light material. [Chemical 1] In formula (I), Z¹ Is a sulfur atom, oxygen atom, selenium atom,
Represents a tellurium atom, a nitrogen atom, or a carbon atom. R is al
Represents a kill group, an aryl group or a heterocyclic group. D is methine
Represents a group necessary to form a dye. Ra and Rb are
Each represents an alkyl group. V¹ And V² Each is a hydrogen atom
Or it represents a monovalent substituent. M represents a charge balanced counter ion
M is 0 or more necessary for neutralizing the charge in the molecule.
Represents the number of Formula (II) [Chemical 2] In formula (II), Z³¹And Z³²Each form a nitrogen-containing heterocycle
Represents the atomic group necessary to However, these have rings
It may be condensed or have a substituent. R ³¹and
R³²Each represents an alkyl group, an aryl group or a heterocyclic group.
The L³¹, L³², L³³, L³⁴, L³⁵, L³⁶And L³⁷Is
Each represents a methine group. p³¹And p³²Is 0 or 1 respectively
Represents. n^ThreeRepresents 0, 1, 2, 3 or 4. M^ThreeIs electric
Represents the load-balancing counterion, m^ThreeNeutralizes the charge in the molecule
This represents a number of 0 or more necessary for the purpose. However, general formula (II)
The compounds represented by general formula (Ia), (Ib), and
And the compound represented by (Ic).